Johari-Goldstein Research Articles

Discovery of collective nonjumping motions leading to Johari–Goldstein process of stress relaxation in model ionic glass

The slow β, or Johari–Goldstein (JG) relaxation process, has been widely observed in glasses and is known to induce the stress relaxation associated with mechanical properties. So far, jumping motions of only a fraction of the particles were believed to contribute to the JG process in glass. However, there is no direct experimental evidence of the atomic-scale images due to the difficulties in microscopic observation. In this study, atomic motions in the quasi-spherical model ionic-glass-former Ca0.4K0.6(NO3)1.4 were microscopically observed with one-angstrom resolution, the highest resolution to date, using X-ray time-domain interferometry. The microscopic experiment directly indicated that most particles underwent angstrom-scale motions in the time scale of the JG relaxation. This result was further supported by molecular dynamics (MD) simulations. A combined study of experiments and MD simulations revealed that most particles contributed to the JG process through unexpected collective nonjumping motions with angstrom-scale displacement, activated by jumping motions of a fraction of particles. The discovery of nonjumping motions by our atomic-scale dynamic observations has considerably advanced our understanding of the puzzling mechanism of the JG process.

Microscopic Observation of the Anisotropy of the Johari-Goldstein-β Process in Cross-Linked Polybutadiene on Stretching by Time-Domain Interferometry.

The strain dependence of the Johari-Goldstein (JG)-β relaxation time, as well as the directional dependence, was systematically investigated for stretched cross-linked polybutadiene using time-domain interferometry. We found that the strain dependence of the JG-β relaxation time is directionally dependent, contrary to expectation: the relaxation time of the JG-β motion, whose displacement is perpendicular to the stretching direction, decreases with stretching, whereas the relaxation time of the parallel JG-β motion changes little. This result is distinct from the previously reported strain dependence of the α relaxation time, where the relaxation time increases isotropically with stretching. Thus, the difference in the strain dependence of the relaxation time between the α and JG-β processes suggests a microscopic origin and requires the modification of the conventional dynamic picture for stretched polymers.

Molecular Dynamics and Near-Tg Phenomena of Cyclic Thioethers.

This article presents the synthesis and molecular dynamics investigation of three novel cyclic thioethers: 2,3-(4'-methylbenzo)-1,4,7,10-tetrathiacyclododeca-2-ene (compound 1), 2,3,14,15-bis(4',4″(5″)-methylbenzo)-1,4,7,10,13,16,19,22,25-octathiacyclotetracosa-2,14-diene (compound 2), and 2,3,8,9-bis(4',4″(5″)-methylbenzo)-1,4,7,10-tetrathiacyclododeca-2,8-diene (compound 3). The compounds exhibit relatively high glass transition temperatures (Tg), which range between 254 and 283 K. This characteristic positions them within the so-far limited category of crown-like glass-formers. We demonstrate that cyclic thioethers may span both the realms of ordinary and sizeable molecular glass-formers, each featuring distinct physical properties. Furthermore, we show that the Tg follows a sublinear power law as a function of the molar mass within this class of compounds. We also reveal multiple dielectric relaxation processes of the novel cyclic thioethers. Above the Tg, their dielectric loss spectra are dominated by a structural relaxation, which originates from the cooperative reorientation of entire molecules and exhibits an excess wing on its high-frequency slope. This feature has been attributed to the Johari-Goldstein (JG) process. Each investigated compound exhibits also at least one intramolecular secondary non-JG relaxation stemming from conformational changes. Their activation energies range from approximately 19 kJ/mol to roughly 40 kJ/mol. Finally, we analyze the high-pressure molecular dynamics of compound 1, revealing a pressure-induced increase in its Tg with a dTg/dp coefficient equal to 197 ± 8 K/GPa.

Breakdown of isochronal superpositioning of [formula omitted]- and [formula omitted]-relaxation times in the van der Waals system – Loratadine

In this paper, high-pressure (HP) dielectric studies on the van der Waals active pharmaceutical ingredient (API) - loratadine (LOR) were carried out. It was found that, surprisingly, the secondary (β) relaxation, which, according to the Coupling Model (CM) predictions, was classified as a Johari-Goldstein (JG) process, separates from the structural (α)-mode with compression (although the shape of the α-peak is invariant to the thermodynamic conditions at constant τα). Consequently, there is a breakdown of the isochronal superpositioning of α- and β- relaxation times (τα and τβ) in this system, which is a typical behavior for the secondary process with intermolecular character. Based on these findings, two possibilities concerning the origin of the β-relaxation in LOR have been proposed: 1) it is a non-JG process (probably originating from fluctuations within cyclic rings of the API molecule), which, however, satisfies the CM predictions; or 2) it is a JG-process, which similarly to a few earlier examined H-bonded compounds (e.g., probucol and sorbitol) is characterized by a different sensitivity to compression when compared to the α-process. Moreover, it was found that the activation entropy for the β-process takes negative values, irrespective of the pressure conditions. That may be interpreted as a result of conformational variation or the loss of translational and rotational degrees of freedom, leading to increased order in API due to densification. The results presented herein give a new insight into the relationship between the structural and secondary relaxations in the close vicinity of the glass transition temperature. Furthermore, they show that HP studies are crucial in elucidating the correlation between these processes.

Fractional Coupling of Primary and Johari-Goldstein Relaxations in a Model Polymer.

A polymer model exhibiting heterogeneous Johari-Goldstein (JG) secondary relaxation is studied by extensive molecular-dynamics simulations of states with different temperature and pressure. Time-temperature-pressure superposition of the primary (segmental) relaxation is evidenced. The time scales of the primary and the JG relaxations are found to be highly correlated according to a power law. The finding agrees with key predictions of the Coupling Model (CM) accounting for the decay in a correlation function due to the relaxation and diffusion of interacting systems. Nonetheless, the exponent of the power law, even if it is found in the range predicted by CM (0<ξ<1), deviates from the expected one. It is suggested that the deviation could depend on the particular relaxation process involved in the correlation function and the heterogeneity of the JG process.

Isochronal superpositioning of the caged dynamics, the α, and the Johari-Goldstein β relaxations in metallic glasses.

The superposition of the frequency dispersions of the structural α relaxation determined at different combinations of temperature T and pressure P while maintaining its relaxation time τα(T, P) constant (i.e., isochronal superpositioning) has been well established in molecular and polymeric glass-formers. Not known is whether the frequency dispersion or time dependence of the faster processes including the caged molecule dynamics and the Johari-Goldstein (JG) β relaxation possesses the same property. Experimental investigation of this issue is hindered by the lack of an instrument that can cover all three processes. Herein, we report the results from the study of the problem utilizing molecular dynamics simulations of two different glass-forming metallic alloys. The mean square displacement 〈Δr2t〉, the non-Gaussian parameter α2t, and the self-intermediate scattering function Fsq,t at various combinations of T and P were obtained over broad time range covering the three processes. Isochronal superpositioning of 〈Δr2t〉, α2t, and Fsq,t was observed over the entire time range, verifying that the property holds not only for the α relaxation but also for the caged dynamics and the JG β relaxation. Moreover, we successfully performed density ρ scaling of the time τα2,maxT,P at the peak of α2t and the diffusion coefficient D(T, P) to show both are functions of ργ/T with the same γ. It follows that the JG β relaxation time τβ(T, P) is also a function of ργ/T since τα2,maxT,P corresponds to τβ(T, P).

Characterization of the secondary relaxations in glass-forming liquids. The contribution of the Starkweather line and of the Coupling Model to the rationalization of TSDC results

This work addresses the study by thermostimulated depolarization currents (TSDC) of Johari-Goldstein (JG) β-relaxations in glass forming systems. Here we analyze the differences between the β-relaxation and the fast secondary (γ, δ, ε, …) relaxations on the one hand, and the α-relaxation on the other.It is shown that TSDC is able to characterize JG although this mobility is often close to, or even partially overlapped with, the α-relaxation.It is also shown that the Starkweather line or zero entropy line (ZEL) can be used as a reference element to identify the secondary relaxations: non-compliance with the ZEL is an indicator of cooperativity.We finally showed that the non-cooperativeness of the Johari-Goldstein relaxation is highlighted by the joint consideration of the Coupling Model and the Starkweather line.

Mutual Information in Molecular and Macromolecular Systems.

The relaxation properties of viscous liquids close to their glass transition (GT) have been widely characterised by the statistical tool of time correlation functions. However, the strong influence of ubiquitous non-linearities calls for new, alternative tools of analysis. In this respect, information theory-based observables and, more specifically, mutual information (MI) are gaining increasing interest. Here, we report on novel, deeper insight provided by MI-based analysis of molecular dynamics simulations of molecular and macromolecular glass-formers on two distinct aspects of transport and relaxation close to GT, namely dynamical heterogeneity (DH) and secondary Johari–Goldstein (JG) relaxation processes. In a model molecular liquid with significant DH, MI reveals two populations of particles organised in clusters having either filamentous or compact globular structures that exhibit different mobility and relaxation properties. In a model polymer melt, MI provides clearer evidence of JG secondary relaxation and sharper insight into its DH. It is found that both DH and MI between the orientation and the displacement of the bonds reach (local) maxima at the time scales of the primary and JG secondary relaxation. This suggests that, in (macro)molecular systems, the mechanistic explanation of both DH and relaxation must involve rotation/translation coupling.

Reconsidering the relation of the JG β-relaxation to the α-relaxation and surface diffusion in ethylcyclohexane

According to the Coupling Model (CM), secondary relaxation belonging to a special class has strong connection to the α-relaxation. These Johari-Goldstein (JG) β-relaxations are predicted to be ubiquitous, and its relaxation time is approximately equal to the primitive relaxation time and the surface diffusion time. These predictions cannot be tested directly in ethylcyclohexane (ECH) because the JG β-relaxation is unresolved and overlapping the α-relaxation to modify its dispersion. To capture the actual dispersion of the α-relaxation we considered surface diffusion data, adiabatic calorimetry data of the JG β-relaxation, and dielectric data of cyanocyclohexane (CNCH). We demonstrated the dispersion of the α-relaxation is actually narrower than known before. The primitive relaxation times calculated are now in agreement with τ JG ( T ) and with τ surface ( T ), and in accord with the CM predictions.

Microscopic understanding of the Johari-Goldstein β relaxation gained from nuclear γ-resonance time-domain-interferometry experiments.

Traditionally the study of dynamics of glass-forming materials has been focused on the structural α relaxation. However, in recent years experimental evidence has revealed that a secondary β relaxation belonging to a special class, called the Johari-Goldstein (JG) β relaxation, has properties strongly linked to the primary α relaxation. By invoking the principle of causality, the relation implies the JG β relaxation is fundamental and indispensable for generating the α relaxation, and the properties of the latter are inherited from the former. The JG β relaxation is observed together with the α relaxation mostly by dielectric spectroscopy. The macroscopic nature of the data allows the use of arbitrary or unproven procedures to analyze the data. Thus the results characterizing the JG β relaxation and the relation of its relaxation time τ_{β} to the α-relaxation time τ_{α} obtained can be equivocal and controversial. Coming to the rescue is the nuclear resonance time-domain-interferometry (TDI) technique covering a wide time range (10^{-9}-10^{-5}s) and a scattering vector q range (9.6-40nm^{-1}). TDI experiments have been carried out on four glass formers, ortho-terphenyl [M. Saito etal., Phys. Rev. Lett. 109, 115705 (2012)10.1103/PhysRevLett.109.115705], polybutadiene [T. Kanaya etal., J. Chem. Phys. 140, 144906 (2014)10.1063/1.4869541], 5-methyl-2-hexanol [F. Caporaletti etal., Sci. Rep. 9, 14319 (2019)10.1038/s41598-019-50824-7], and 1-propanol [F. Caporaletti etal., Nat. Commun. 12, 1867 (2021)10.1038/s41467-021-22154-8]. In this paper the TDI data are reexamined in conjunction with dielectric and neutron scattering data. The results show the JG β relaxation observed by dielectric spectroscopy is heterogeneous and comprises processes with different length scales. A process with a longer length scale has a longer relaxation time. TDI data also prove the primitive relaxation time τ_{0} of the coupling model falls within the distribution of the TDI q-dependent JG β-relaxation times. This important finding explains why the experimental dielectric JG β-relaxation times τ_{β}(T,P) is approximately equal to τ_{0}(T,P) as found in many glass formers at various temperature T and pressure P. The result, τ_{β}(T,P)≈τ_{0}(T,P), in turn explains why the ratio τ_{α}(T,P)/τ_{β}(T,P) is invariant to changes of T and pressure P at constant τ_{α}(T,P), the α-relaxation time.

Dynamic heterogeneity, cooperative motion, and Johari-Goldstein [Formula: see text]-relaxation in a metallic glass-forming material exhibiting a fragile-to-strong transition.

We investigate the Johari-Goldstein (JG) [Formula: see text]-relaxation process in a model metallic glass-forming (GF) material ([Formula: see text]), previously studied extensively by both frequency-dependent mechanical measurements and simulation studies devoted to equilibrium properties, by molecular dynamics simulations based on validated and optimized interatomic potentials with the primary aim of better understanding the nature of this universal relaxation process from a dynamic heterogeneity (DH) perspective. The present relatively low temperature and long-time simulations reveal a direct correspondence between the JG [Formula: see text]-relaxation time [Formula: see text] and the lifetime of the mobile particle clusters [Formula: see text], defined as in previous DH studies, a relationship dual to the corresponding previously observed relationship between the [Formula: see text]-relaxation time [Formula: see text] and the lifetime of immobile particle clusters [Formula: see text]. Moreover, we find that the average diffusion coefficient D nearly coincides with [Formula: see text] of the smaller atomic species (Al) and that the 'hopping time' associated with D coincides with [Formula: see text] to within numerical uncertainty, both trends being in accord with experimental studies. This indicates that the JG [Formula: see text]-relaxation is dominated by the smaller atomic species and the observation of a direct relation between this relaxation process and rate of molecular diffusion in GF materials at low temperatures where the JG [Formula: see text]-relaxation becomes the prevalent mode of structural relaxation. As an unanticipated aspect of our study, we find that [Formula: see text] exhibits fragile-to-strong (FS) glass formation, as found in many other metallic GF liquids, but this fact does not greatly alter the geometrical nature of DH in this material and the relation of DH to dynamical properties. On the other hand, the temperature dependence of the DH and dynamical properties, such as the structural relaxation time, can be significantly altered from 'ordinary' GF liquids.

Johari–Goldstein Heterogeneous Dynamics in a Model Polymer

The heterogeneous character of the Johari-Goldstein (JG) relaxation is evidenced by molecular-dynamics simulation of a model polymer system. A double-peaked evolution of dynamic heterogeneity (DH), with maxima located at JG and structural relaxation time scales, is observed and mechanistically explained. {The short-time single-particle displacement during JG relaxation weakly correlates with the long-time one observed during structural relaxation}.

Fast dynamics in a model metallic glass-forming material.

We investigate the fast β- and Johari-Goldstein (JG) β-relaxation processes, along with the elastic scattering response of glass-forming (GF) liquids and the boson peak, in a simulated Al-Sm GF material exhibiting a fragile-strong (FS) transition. These dynamical processes are universal in "ordinary" GF fluids and collectively describe their "fast dynamics," and we find these relaxation processes also arise in a GF liquid exhibiting a FS transition. String-like particle motion, having both an irreversible and a reversible nature (stringlets) component, occurs in the fast-dynamics regime, corresponding to a ps timescale. String-like collective motion associated with localized unstable modes facilitates irreversible and intermittent particle "jumping" events at long times associated with the JG β-relaxation process, while stringlets associated with localized stable modes and corresponding perfectly reversible atomic motion give rise to the boson peak. To further clarify the origin of the boson peak, we calculate the density of states for both the stringlet particles and the "normal" particles and find that the stringlet particles give rise to a boson peak, while the normal atoms do not. The growth of stringlets upon heating ultimately also leads to the "softening" of these excitations, and the boson peak frequency and shear modulus drop in concert with this softening. The growth of string-like collective motion upon heating in the fast-dynamics regime is further shown to be responsible for the growth in the intensity of the fast relaxation process. Relaxation in cooled liquids clearly involves a hierarchy of relaxation processes acting on rather different timescales and spatial scales.

Molecular dynamics in the supercooled liquid and glassy states of bezafibrate and binary mixture of fenofibrate

Two solubility limited pharmaceuticals bezafibrate and fenofibrate, belonging to BCS class II drugs, were compared, by investigating molecular dynamics of the former and compared with the neat and as a probe in an apolar host polystyrene of mole. wt. 800 (PS800) of the latter by broadband dielectric spectroscopy (BDS), other supporting thermal and spectroscopic experimental means and density functional theory (DFT) calculations. The BDS experiments from frozen glassy state to vibrant molten state of the title drugs were done to explore the role of parameters describing their complex molecular dynamics and the stabiliy of amorphous phase, such as glass transition temperature (Tg), temperature dependence of α-relaxation times (τα), width of structural dispersion and its role on the occurrence of Johari-Goldstein (JG) β-relaxation, fragility index (m) and apparent activation energy of secondary processes. Realizing that most of the pharmaceuticals have narrow α-dispersion which limits the visibility of JG β-relaxation as a separate process in the dielectric window, to resolve the conundrum, we have further explored the amorphous dynamics of fenofibrate as a probein an apolar host polystyrene of molecular weight 800 (PS800) having higher Tg than the polar probe. The Tg of bezafibrate and PS800-fenofibrate mixture were determined to be 298 K and 275 K respectively, whereas the fractional exponent of Kohlrausch–Williams–Watts function βKWW of bezafibrate was determined to be 0.68 which is closer to that of fenofibrate, whereas that of PS800-fenofibrate mixture was found to be much broader with a value of 0.39, all in the vicinity of Tg. Even though βKWW decreased in binary mixture of fenofibrate when compared to its pure form due to concentration fluctuations and other aspects, but cold crystallization tendency was absent and Tg is elevated than that of fenofibrate. Due to higher Tg than that of fenofibrate, amorphous bezafibrate is more stable than fenofibrate. Finally, using quantum computational calculations using DFT, the relevant flexible parts of the two drug molecules, whose motions manifests the secondary γ-relaxation was identified by calculating potential energy barriers and dipole moments on relaxed dihedral angle scans, as no experimental technique is available for this purpose.

Invariance of the relation between α relaxation and β relaxation in metallic glasses to variations of pressure and temperature

Dielectric relaxation experiments performed at ambient and elevated pressures P in molecular, ionic, and polymeric glass formers have established that the relation of the Johari-Goldstein (JG) \ensuremath{\beta}-relaxation time ${\ensuremath{\tau}}_{\ensuremath{\beta}}(T,P)$ to the \ensuremath{\alpha}-relaxation time ${\ensuremath{\tau}}_{\ensuremath{\alpha}}(T,P)$ is invariant to changes of T and P while the latter is kept constant. This property of the JG \ensuremath{\beta} relaxation is remarkable despite the fact that the invariance of the ratio ${\ensuremath{\tau}}_{\ensuremath{\beta}}(T,P)/{\ensuremath{\tau}}_{\ensuremath{\alpha}}(T,P)$ from experiment is sometimes approximate because the \ensuremath{\beta} relaxation is composed of a distribution of processes, and the ${\ensuremath{\tau}}_{\ensuremath{\beta}}(T,P)$ determined can be arbitrary. The property indicates the fundamental importance of the JG \ensuremath{\beta} relaxation and it cannot be neglected whenever the \ensuremath{\alpha} relaxation is considered. Notwithstanding, the property has not been checked on whether it applies to metallic glasses. Conventional experiment techniques cannot fulfill the task, and the alternative is molecular dynamics simulations. In this paper we report the results of molecular dynamics simulations of dynamical mechanical spectroscopy performed on two very different metallic glasses, $\mathrm{Z}{\mathrm{r}}_{50}\mathrm{C}{\mathrm{u}}_{50}$ and $\mathrm{N}{\mathrm{i}}_{80}{\mathrm{P}}_{20}$, at different pressures P. The JG \ensuremath{\beta} relaxation appears as an excess wing on the low-temperature side of the \ensuremath{\alpha} loss peak at ${T}_{\ensuremath{\alpha},P}$ in the isochronal loss modulus spectra ${{E}_{P}}^{\ensuremath{''}}(T)$. On the other hand, the isochronal non-Gaussian parameter $\ensuremath{\alpha}{2}_{P}(T)$ peaks at the temperature ${T}_{\ensuremath{\alpha}2,P}$ different from ${T}_{\ensuremath{\alpha},P}$ of ${{E}^{\ensuremath{''}}}_{P}(T)$. From the fact that ${T}_{\ensuremath{\alpha}2,P}$ is significantly lower than ${T}_{\ensuremath{\alpha},P}$, we identified the peak temperature ${T}_{\ensuremath{\alpha}2,P}$ of $\ensuremath{\alpha}{2}_{P}(T)$ with the JG \ensuremath{\beta} relaxation, and hence the JG \ensuremath{\beta} relaxation is fully resolved by studying the isochronal non-Gaussian parameter $\ensuremath{\alpha}{2}_{P}(T)$. After scaling temperature by ${T}_{\ensuremath{\alpha},P}$, the normalized ${{E}_{P}}^{\ensuremath{''}}(T/{T}_{\ensuremath{\alpha},P})$ and $\ensuremath{\alpha}{2}_{P}(T/{T}_{\ensuremath{\alpha},P})$ both show superposition of data taken at various pressures for all $T/{T}_{\ensuremath{\alpha},P}$ covering the JG \ensuremath{\beta} relaxation and the \ensuremath{\alpha} relaxation. Moreover the ratio ${T}_{\ensuremath{\alpha}2,P}/{T}_{\ensuremath{\alpha},P}$ is invariant to changes of T and P while ${\ensuremath{\tau}}_{\ensuremath{\alpha}}(T,P)$ is maintained constant. Thus we have verified for two different metallic glasses, $\mathrm{Z}{\mathrm{r}}_{50}\mathrm{C}{\mathrm{u}}_{50}$ and $\mathrm{N}{\mathrm{i}}_{80}{\mathrm{P}}_{20}$, that ${\ensuremath{\tau}}_{\ensuremath{\alpha}}(T,P)/{\ensuremath{\tau}}_{\ensuremath{\beta}}(T,P)$ is invariant to changes of T and P at constant ${\ensuremath{\tau}}_{\ensuremath{\alpha}}(T,P)$, as found in soft matter.

Accounts of the changes in dynamics of hydrogen-bonded materials by pressure, nanoconfinement, and hyperquenching.

A hydrogen-bonding network or hydrogen-bonded cluster is formed in many hydrogen-bonded glass formers. It determines the dynamics of structural α relaxation and the Johari-Goldstein (JG) β relaxation because breaking of hydrogen bonds is the prerequisite. However, the networks and clusters can be substantially reduced or totally removed in the liquid state by high temperature accompanying the applied high pressure in experiments, and in the glassy state by hyperquenching the liquid under pressure. By confining the glass former in nanometer spaces, the extended network cannot form, and in addition the finite size effect limits the growth of the length scale of the α relaxation on lowering temperature. Any of these actions will modify the structure of the original hydrogen-bonded glass former, and also the intermolecular interaction governing the relaxation processes. Consequently the dynamics of the structural α relaxation and the JG β relaxation, as well as the relation between the two processes, are expected to change. An important advance in the study of the dynamics of glass-forming materials is the existence of the strong connection between the α relaxation and the JG β relaxation. In particular, the ratio of their relaxation times, t_{α}(T)/t_{β}(T), is quantitatively determined by the exponent of the Kohlrausch relaxation function of the α relaxation. This property is valid in hydrogen-bonded glass formers as well as in non-hydrogen-bonded glass formers. The interesting question is whether this property continues to hold after the hydrogen-bonded glass former has been modified by high temperature under high pressure, nanoconfinement, and hyperquenching under pressure. Remarkably, the answer is positive as concluded from the analyses of the data in several hydrogen-bonded glass formers reported in this paper. So far the main theoretical explanation of this property has been the coupling model.

Clarifying the nature of the Johari-Goldstein β-relaxation and emphasising its fundamental importance

ABSTRACT Since 1998 the primitive relaxation time τ 0(T,P) of the Coupling Model (CM) and the Johari-Goldstein (JG) β-relaxation time τJG (T,P) are shown approximately equal in many glass-formers. The CM relation between τ 0(T,P) and τα (T,P) at any T and P is exact. Additionally from the CM relation τα (T,P)/τ 0(T,P) is exactly invariant to variations of T and P while τα (T,P) is kept constant, and τ 0 is exactly a function of ρ γ/T like τα . However, since τJG (T,P) ≈ τ 0(T,P), the exact invariance of τα (T,P)/τ 0(T,P) leads to approximate invariance of τα (T,P)/τJG (T,P), and τJG is approximately a function of ρ γ/T. Notwithstanding, the CM prediction of the approximate relations between τβ and τα were mistaken as exact relations by some researchers. In this paper, we remove this misunderstanding by demonstrating via simulations and experiments that the JG β-relaxation is comprised of processes with different length-scales and degrees of cooperativity, and the process is heterogeneous. The distribution of processes makes τJG (T,P) equivocal, because it is just a single relaxation time used to represent the different processes within the distribution, which may change on varying T and P, at constant τα (T,P). The problem is compounded if the β-relaxation is not resolved, and fitting procedure used to extract τJG (T,P) and τα (T,P). Despite the relations of τJG (T,P) to τα (T,P) are approximate, we show these properties of τJG (T,P) are truly remarkable, fundamental, general, and important.

Influence of the Internal Structure and Intermolecular Interactions on the Correlation between Structural (α) and Secondary (β-JG) Relaxation below the Glass Transition Temperature in Neat Probucol and Its Binary Mixtures with Modified Saccharides.

Broadband dielectric spectroscopy (BDS) has been used to study the molecular dynamics and aging process in neat probucol (PRO) as well as its binary mixtures with selected acetylated saccharides. In particular, we applied the Casalini and Roland approach to determine structural relaxation times in the glassy state of the examined systems (so-called isostructural times, τiso). Next, using the calculated τiso, primitive relaxation times of the coupling model were obtained and compared to the experimental secondary β (Johari-Goldstein (JG) type) relaxation times. Interestingly, it turned out that there is a correlation between the β-JG and the structural (α)-relaxation processes below the glass transition temperature (T < Tg) in each investigated sample. This is a new observation compared to previous studies demonstrating that such a relationship exists only in the supercooled liquid state of neat PRO. Moreover, it was revealed that the stretching parameters obtained from the aging procedure are very close to the ones determined by fitting the dielectric data above the Tg with the use of the Kohlrausch-Williams-Watts function, indicating that the aging process is governed by the α-relaxation. Complementary Fourier transform infrared and X-ray diffraction measurements allowed us to find a possible reason for these findings. It was demonstrated that although there are very weak intermolecular interactions between PRO and modified saccharides, the intra- and intermolecular structure of PRO is practically unaffected by the presence of modified saccharides.

Coincident Correlation between Vibrational Dynamics and Primary Relaxation of Polymers with Strong or Weak Johari-Goldstein Relaxation.

The correlation between the vibrational dynamics, as sensed by the Debye-Waller factor, and the primary relaxation in the presence of secondary Johari-Goldstein (JG) relaxation, has been investigated through molecular dynamics simulations. Two melts of polymer chains with different bond length, resulting in rather different strength of the JG relaxation are studied. We focus on the bond-orientation correlation function, exhibiting higher JG sensitivity with respect to alternatives provided by torsional autocorrelation function and intermediate scattering function. We find that, even if changing the bond length alters both the strength and the relaxation time of the JG relaxation, it leaves unaffected the correlation between the vibrational dynamics and the primary relaxation. The finding is in harmony with previous studies reporting that numerical models not showing secondary relaxations exhibit striking agreement with experimental data of polymers also where the presence of JG relaxation is known.

Breakdown of the isochronal structural (α) and secondary (JG β) exact superpositioning in probucol - A low molecular weight pharmaceutical

In this paper, Broadband Dielectric Spectroscopy (BDS) has been applied to study the molecular dynamics of the two active pharmaceutical ingredients (APIs), probucol (PRO) and droperidol (DRO), above and below the glass transition temperature, at varying thermodynamic conditions. We found that the structural (α)-relaxation process in both compounds is sensitive to compression. It was reflected in the high pressure coefficients of the glass transition temperature, dTg/dp = 227 K/GPa and dTg/dp = 427 K/GPa for DRO and PRO, respectively. In this context, it is worthwhile to emphasize that dTg/dp calculated for the latter API is the highest reported to date for the low molecular weight glass formers. Furthermore, the data collected upon squeezing samples revealed that the pressure dependence of the relaxation times of the Johari Goldstein (JG) β-process in PRO is weaker with respect to that of structural relaxation. Thus, a breakdown of exact superposition of both modes has been noted. A slightly different scenario was observed in DRO, where relaxation times of the secondary non-JG γ-process, obtained at different T and p, plotted versus Tg/T, collapsed forming a single curve. A breakdown of exact isochronal superpositioning of α- and JG β-relaxation times at varying thermodynamic conditions in PRO, that is weakly H-bonded low molecular weight glass former, is in accordance with the data reported for the strongly associating compounds (e.g., sorbitol). Moreover, recently a similar scenario has been observed for some polymers, i.e., 1,4-polybutadiene (PBD) (Ransom et al., 2018), poly(methyl methacrylate) (PMMA) (Casalini and Roland, 2013) and polyisoprene (PI) (Kołodziej et al., 2018). This phenomenon, which is consistent with the approximate invariance of the ratio of these two relaxation times to change of thermodynamics conditions (as predicted by the Coupling Model), was assigned to the increasing torsional rigidity of the macromolecule backbone or alternatively to the non-uniform responses to variations of temperature and pressure of the distributed modes composing the JG β-process, resulting in changes of the spectral shape and different fβ(p,T) obtained from the fitting procedure. One can suppose that due to the variation in the population of weak H-bonds at elevated pressure in PRO, the latter effect might be enhanced, contributing to the observed experimental finding. Finally, the data reported herein emphasize the impact of molecular aspects related to specific interactions on the correlation between α- and JG β-relaxation at varying T and p conditions.