Arriving at the most plausible interpretation of the dielectric spectra of glycerol with help from quasielastic γ-ray scattering time-domain interferometry.

Glycerol is one of the glass-forming liquids selected by Robert H. Cole in 1950 to start his study of molecular dynamics by dielectric spectroscopy. Seventy-one years have gone by and remarkably no consensus has been reached on the nature and identity of the relaxation processes observed in the dielectric spectra. The macroscopic dielectric relaxation data allow different interpretations to yield contrasting results, and it is not possible to determine which one is most plausible. Coming to the rescue is the application of the nuclear γ-resonance time-domain interferometry (TDI) to glycerol by Saito et al. [Phys. Rev. E 105, L012605 (2022)10.1103/PhysRevE.105.L012605]. Their microscopic TDI data potentially can decide which interpretation of the dielectric spectra of glycerol is most plausible. The attempt was made by Saito et al., but there is a problem in their analysis of the dielectric data of glycerol and hence their conclusion is untenable. In this paper, we critically compare four major interpretations with the TDI data in an effort to identify the most plausible interpretation of the relaxation processes constituting the dielectric spectra of glycerol.

Comparative analysis of dielectric, shear mechanical and light scattering response functions in polar supercooled liquids.

The studies of molecular dynamics in the vicinity of liquid-glass transition are an essential part of condensed matter physics. Various experimental techniques are usually applied to understand different aspects of molecular motions, i.e., nuclear magnetic resonance (NMR), photon correlation spectroscopy (PCS), mechanical shear relaxation (MR), and dielectric spectroscopy (DS). Universal behavior of molecular dynamics, reflected in the invariant distribution of relaxation times for different polar and weekly polar glass-formers, has been recently found when probed by NMR, PCS, and MR techniques. On the other hand, the narrow dielectric permittivity function ε*(f) of polar materials has been rationalized by postulating that it is a superposition of a Debye-like peak and a broader structural relaxation found in NMR, PCS, and MR. Herein, we show that dielectric permittivity representation ε*(f) reveals details of molecular motions being undetectable in the other experimental methods. Herein we propose a way to resolve this problem. First, we point out an unresolved Johari-Goldstein (JG) ß-relaxation is present nearby the α-relaxation in these polar glass-formers. The dielectric relaxation strength of the JG ß-relaxation is sufficiently weak compared to the α-relaxation so that the narrow dielectric frequency dispersion faithfully represents the dynamic heterogeneity and cooperativity of the α-relaxation. However, when the other techniques are used to probe the same polar glass-former, there is reduction of relaxation strength of α-relaxation relative to that of the JG ß relaxation as well as their separation. Consequently the α relaxation appears broader in frequency dispersion when observed by PCS, NMR and MR instead of DS. The explanation is supported by showing that the quasi-universal broadened α relaxation in PCS, NMR and MR is captured by the electric modulus M*(f) = 1/ε*(f) representation of the dielectric measurements of polar and weakly polar glass-formers, and also M*(f) compares favorably with the mechanical shear modulus data G*(f).

Microscopic understanding of the Johari-Goldstein ß 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 ß relaxation belonging to a special class, called the Johari-Goldstein (JG) ß relaxation, has properties strongly linked to the primary α relaxation. By invoking the principle of causality, the relation implies the JG ß relaxation is fundamental and indispensable for generating the α relaxation, and the properties of the latter are inherited from the former. The JG ß 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 ß relaxation and the relation of its relaxation time τ_{ß} 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 et al., Phys. Rev. Lett. 109, 115705 (2012)10.1103/PhysRevLett.109.115705], polybutadiene [T. Kanaya et al., J. Chem. Phys. 140, 144906 (2014)10.1063/1.4869541], 5-methyl-2-hexanol [F. Caporaletti et al., Sci. Rep. 9, 14319 (2019)10.1038/s41598-019-50824-7], and 1-propanol [F. Caporaletti et al., 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 ß 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 ß-relaxation times. This important finding explains why the experimental dielectric JG ß-relaxation times τ_{ß}(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_{ß}(T,P)≈τ_{0}(T,P), in turn explains why the ratio τ_{α}(T,P)/τ_{ß}(T,P) is invariant to changes of T and pressure P at constant τ_{α}(T,P), the α-relaxation time.

The origin of the faster mechanism of partial enthalpy recovery deep in the glassy state of polymers.

A novel finding made by Cangialosi and coworkers in the physical aging of several polymers way below the glass transition temperature Tg is that equilibrium recovery occurs by reaching a plateau in the enthalpy with partial enthalpy recovery. This observation points to the existence of a much faster mechanism capable of partial equilibrium recovery deep in the glassy state. A similar phenomenon was found in different glassy materials. The generality of the phenomenon indicates that the faster mechanism of equilibrium recovery is universal and fundamental. In this paper the faster mechanism is identified to be the universal JG ß-relaxation having dynamic and thermodynamic properties analogous to the α-relaxation, and thus capable of effecting enthalpy and volume recovery far below Tg in several high-Tg polymers. The JG ß-relaxation is also the mechanism responsible for the first step of two steps in the approach to equilibrium found in another polymer with much lower Tg. The Coupling Model is used to explain why the first step transpires far below Tg in some polymers but much closer to Tg in another polymer.

Why the Brillouin Light Scattering Relaxation Times of Molten Zinc Chloride Are Shorter and Weaker in Temperature Dependence than the Structural Relaxation Times from Depolarized Light and Neutron Spin Echo Spectroscopy.

A longstanding problem in the Brillouin light scattering (BLS) study of polymers is the relaxation times τBLS(T) being more than an order of magnitude shorter than the α-relaxation times τα(T) determined by dielectric, depolarized light scattering (DLS), and molecular dynamics simulations. In tackling the problem, τBLS(T) was identified with the relaxation time τ0(T) of the primitive relaxation in the coupling model, which can be calculated from τα(T) and the stretch exponent ßK of the Kohlrausch correlation function for the α-relaxation.. The problem was solved by finding that indeed τ0(T) is in good agreement with τBLS(T). A recent work performed the neutron spin echo study of the structural α-relaxation of the network ionic liquid ZnCl2 and found the same anomaly as polymers. The α-relaxation time τNSE(T) from neutron spin echo (NSE) as well as the α-relaxation time τDLS(T) from DLS of ZnCl2 are much longer than τBLS(T) from BLS obtained before by several research groups. The finding of the same anomaly in ZnCl2 and polymers with very different chemical and physical structures offers an opportunity to critically test the explanation given before. The test was carried out by calculating the primitive relaxation times τ0,DLS(T) and τ0,NSE(T) from τDLS(T) and τNSE(T), respectively, in zinc chloride. Good agreements of τBLS(T) from BLS with τ0,DLS(T) and τ0,NSE(T) were found and thus the explanation given for polymers remains valid for ZnCl2. The test was extended to glycerol by comparing τBLS(T) with τ0,ICNS(T) and τ0,CNS(T) calculated from the α-relaxation time τICNS(T) and τCNS(T) from incoherent and coherent neutron scattering, respectively. There is good agreement between τBLS(T) and τ0,ICNS(T) in glycerol. There is also semiquantitative agreement of τBLS(T) with τ0,DS(T) from dielectric spectroscopy as well as τ0,CNS(T). Thus, the explanation for polymers is verified in the two very different glass formers, ZnCl2 and glycerol, and it is an advancement in the application of BLS to study the dynamics of glass formers.

Broadband Dielectric Study of Sizable Molecular Glass Formers: Relationship Between Local Structure and Dynamics.

In this Letter we report significant differences in the dielectric behavior of four nonpolymeric and sizable glass-forming molecules with related chemical structures. They belong to the recently constituted class of sizable glass-formers [Jedrzejowska et al. Phys. Rev. E: Stat. Phys., Plasmas, Fluids, Relat. Interdiscip. Top. 2020, 101, 010603], for which the pattern of change in dielectric properties with structure has not yet been fully discovered. In the present study we tackle the fundamental problem of the structure-dynamics relationship. It was made possible by judicious choice of investigated systems with the values of dipole moments purposely kept at about the same level, and the only difference is the structure of the terminal substituents applied. The remarkable effect revealed by broadband dielectric spectroscopy is a large difference in the frequency dispersion of the α-relaxation for the systems studied. This interesting finding can be rationalized by the results of X-ray diffraction, clearly indicating the dissimilarities in the local intermolecular structure.

Isochronal superpositioning of the caged dynamics, the α, and the Johari-Goldstein ß 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) ß 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 ß 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 ß relaxation time τß(T, P) is also a function of ργ/T since τα2,maxT,P corresponds to τß(T, P).

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) ß 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 ß 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 ß relaxation. In particular, the ratio of their relaxation times, t_{α}(T)/t_{ß}(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.

Isochronal Superposition of the Structural α-Relaxation and Invariance of Its Relation to the ß-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 ßKWW 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 ß-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)/τß(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 ß-relaxations in pure small-molecule glass-formers.

The structural α-relaxation times of prilocaine confined in 1 nm pores of molecular sieves: quantitative explanation by the coupling model.

The molecular glass-former and pharmaceutical, prilocaine, distinguishes itself by exhibiting seven general and fundamental dynamic and thermodynamic properties [Z. Wojnarowska, et al., J. Phys. Chem. B, 2015, 39, 12699.], all of which have been explained using the coupling model. What has not been studied before are the changes in properties of the structural α-relaxation of prilocaine when subjected to extreme nano-confinement in spaces with a size of about 1 nm. Recently, Ruis et al. [G. N. Ruiz, et al., Phys. Chem. Chem. Phys., 2019, 21, 15576.] measured the α-relaxation times, τα,conf(T), of prilocaine confined in 1 nm pores of molecular sieves. They found that τα,conf(T) are significantly reduced from those of bulk prilocaine, τα,bulk(T), and assume a weaker temperature dependence. The data in toto pose a challenge for any theory of glass transition to explain quantitatively. The coupling model (CM) was applied to this problem to predict the α-relaxation times of prilocaine when cooperativity is removed, which is expected because only a few prilocaine molecules can fit into the 1 nm pores. The results from the CM are in quantitative agreement with the experimental values of τα,conf(T) and the temperature dependence. The success is nontrivial because no other extant theory can do the same to the best of our knowledge.

New paradigm of dielectric relaxation of sizable and rigid molecular glass formers.

In this Rapid Communication we report the unusual dynamics of planar, rigid, and anisotropy glass-forming molecules of unusually large size by dielectric spectroscopy by using two examples. The size of the molecules is much larger than the dipolar moiety located at the end of the longer axis of each molecule. The observed dynamics deviates strongly from the anticorrelation between ß_{KWW} (fractional exponent of the Kohlrausch-Williams-Watts function) and dielectric strength, Δɛ(T_{g}), established generally for small van der Waals molecular glass formers. Moreover, the dynamics of the two large molecules differ greatly, albeit the difference is the dipole moment being orthogonal or parallel to the longer axis of the molecules. The drastic variation in dielectric response of the two materials coming from different portions of the structural α-relaxation spectrum is probed by the dipole. Thus, the new behavior opens up a new research area of the dynamics and thermodynamics of nonpolymeric sizable molecules, the dielectric response of which can be varied by the design of the dipole moiety.

Predicting the α-relaxation time of glycerol confined in 1.16 nm pores of zeolitic imidazolate frameworks.

Uhl et al. [J. Chem. Phys., 2019, 150, 024504] studied the molecular dynamics of glycerol confined in a microporous zeolitic imidazolate framework (ZIF-8) with well-defined pore diameters of 1.16 nm by broadband dielectric spectroscopy. Of interest is a fast process in the central part of the pores identified as the α-relaxation of the confined supercooled glycerol with relaxation times τα,conf(T) reduced from τα,bulk(T) of bulk glycerol and having a temperature dependence different from the super-Arrhenius temperature of the latter. The focus of Uhl et al. was relating the confined molecular dynamics to the cooperativity length scales Lcorr(T) of molecular motion above the glass transition, and deducing the limiting high-temperature value of the correlation length of about 1.22 nm. Not yet considered by anyone are the observed values of τα,conf(T) and temperature dependence. Since the cooperativity length scales Lcorr(T) were found to be larger than the pore size of ZIF-8 over the temperature range studied and the density of the glycerol in the pore is possibly lower than the bulk, the cooperativity of the α-relaxation of glycerol confined in ZIF-8 is drastically reduced. Thus, within the framework of the Coupling Model (CM), τα,conf(T) should be nearly the same as the primitive relaxation time τ0(T) for glycerol when devoid of intermolecular coupling and cooperativity. Consistent with the absence of cooperativity of the glycerol confined in ZIF-8, we find the calculated τα,conf(T) are either the same or slightly longer than the calculated values of τ0(T). The quantitative prediction of the CM is verified. At this time we know of no other theory that can make such a quantitative prediction.

Glassy Dynamics and Translational-Rotational Coupling of an Ionically Conducting Pharmaceutical Salt-Sodium Ibuprofen.

In this work, we study the structural dipolar relaxation and ionic conductivity relaxation in an ionized derived from a nonionized glass former. The latter is the salt form of a well-studied active pharmaceutical ingredient, sodium ibuprofen, and the former is ibuprofen. Quantum mechanical calculations were employed to study the variation in its molecular electrostatic potentials, and its spatial extent on its salt formation with Na+ ions. Measurements have been made using differential scanning calorimetry and broadband dielectric spectroscopy, and the characterization is assisted by density functional theory. The dielectric data contain information on both ionic and dipolar molecular mobility of NaIb and were extracted by representation in terms of the electric modulus and permittivity. A secondary ß-conductivity relaxation coexists with the primary α-conductivity relaxation. By use of the coupling model, we show that the ß-conductivity relaxation is connected to the α-conductivity relaxation and is the analogue of the relation of the Johari-Goldstein ß-relaxation to the structural α-relaxation, shown valid also in ibuprofen. This remarkable result has an impact on the fundamental understanding of the dynamics of ionic conductivity. By representing the data as permittivity, a dipolar ß-relaxation was found to have practically the same relaxation times as the ß-conductivity relaxation in the glassy state and translational-rotational coupling is valid at a more local secondary relaxation level. However, the α-conductivity relaxation decouples from structural α-relaxation because the structural glass transition temperature is lower than the conductivity counterpart by 29 K. These are novel findings. The study elucidates the effects on the dynamics by the change in the nature of bonding and in size on introducing sodium ions to ibuprofen in the glassy and supercooled liquid states.

The JG ß-relaxation in water and impact on the dynamics of aqueous mixtures and hydrated biomolecules.

Although by now the glass transition temperature of uncrystallized bulk water is generally accepted to manifest at temperature Tg near 136 K, not much known are the spectral dispersion of the structural α-relaxation and the temperature dependence of its relaxation time τα,bulk(T). Whether bulk water has the supposedly ubiquitous Johari-Goldstein (JG) ß-relaxation is a question that has not been answered. By studying the structural α-relaxation over a wide range of temperatures in several aqueous mixtures without crystallization and with glass transition temperatures Tg close to 136 K, we deduce the properties of the α-relaxation and the temperature dependence of τα,bulk(T) of bulk water. The frequency dispersion of the α-relaxation is narrow, indicating that it is weakly cooperative. A single Vogel-Fulcher-Tammann (VFT) temperature dependence can describe the data of τα,bulk(T) at low temperatures as well as at high temperatures from neutron scattering and GHz-THz dielectric relaxation, and hence, there is no fragile to strong transition. The Tg-scaled VFT temperature dependence of τα,bulk(T) has a small fragility index m less than 44, indicating that water is a "strong" glass-former. The existence of the JG ß-relaxation in bulk water is supported by its equivalent relaxation observed in water confined in spaces with lengths of nanometer scale and having Arrhenius T-dependence of its relaxation times τconf(T). The equivalence is justified by the drastic reduction of cooperativity of the α-relaxation in nanoconfinement and rendering it to become the JG ß-relaxation. Thus, the τconf(T) from experiments can be taken as τß,bulk(T), the JG ß-relaxation time of bulk water. The ratio τα,bulk(Tg)/τß,bulk(Tg) is smaller than most glass-formers, and it corresponds to the Kohlrausch α-correlation function, exp[-(t/τα,bulk)1-n], having (1-n) = 0.90. The dielectric data of many aqueous mixtures and hydrated biomolecules with Tg higher than that of water show the presence of a secondary ν-relaxation from the water component. The ν-relaxation is strongly connected to the α-relaxation in properties, and hence, it belongs to the special class of secondary relaxations in glass-forming systems. Typically, its relaxation time τν(T) is longer than τß,bulk(T), but τν(T) becomes about the same as τß,bulk(T) at sufficiently high water content. However, τν(T) does not become shorter than τß,bulk(T). Thus, τß,bulk(T) is the lower bound of τν(T) for all aqueous mixtures and hydrated biomolecules. Moreover, it is τß,bulk(T) but not τα(T) that is responsible for the dynamic transition of hydrated globular proteins.

Relations between the Structural α-Relaxation and the Johari-Goldstein ß-Relaxation in Two Monohydroxyl Alcohols: 1-Propanol and 5-Methyl-2-hexanol.

The hydrogen-bonded monohydroxyl alcohols form a large class of glass formers studied more than one hundred years, and still the structure and dynamics have continued to be a research problem. Recent advance suggests a hydrogen-bonded transient supramolecular structure, which is the origin of the Debye relaxation dominating the dielectric loss spectra of many monohydroxyl alcohols. Obscured by the slower Debye relaxation, the structural α-relaxation is either not resolved or showing up as a shoulder and the supposedly universal Johari-Goldstein (JG) ß-relaxation is not always observed. Thus, properties of the α-relaxation and the JG ß-relaxation as well as the strong connection between the two relaxations generally observed in other classes of glass formers are not commonly known in the monohydroxyl alcohols. Notwithstanding, extremely broadband dielectric relaxation and high-precision light scattering experiments published recently have resolved the α-relaxation and a secondary relaxation in two archetypal monohydroxyl alcohols, 1-propanol and 5-methyl-2-hexanol (5M2H) by Gabriel et al. We analyzed their experimental data and applied the Coupling Model to show that the secondary relaxations in 1-propanol and 5M2H are JG ß-relaxations with strong connection to the α-relaxation. The result is novel because it is not known before whether the secondary relaxations of these two monohydroxyl alcohols are JG ß-relaxation involving the entire molecule or are intramolecular relaxations. On the basis of this conclusion, we predict that the secondary relaxation is pressure-dependent and the ratio τß( T, P)/τα( T, P) is invariant to variations of P and T, whereas τα( T, P) is maintained constant and provided that the frequency dispersion of the α-relaxation is also constant. The prediction is compared with the dielectric data of 5M2H at elevated pressures. On the basis of the identification of monohydroxyl alcohols as short-chain polymeric liquids by others, an explanation of the stronger T and P dependences of τα( T, P) than the Debye relaxation time τD( T, P) is given.

Deviations of dynamic parameters characterizing enthalpic and dielectric relaxations in glass forming alkyl phosphates.

In our recent study [T. Wu et al., J. Chem. Phys. 147, 134501 (2017)], an alkyl phosphate glass former was studied and it suggested that the enthalpy relaxation involving the motions of all parts of the molecule is global, while the dielectric relaxation detects the local rotation of the polar core. In this work, we study a series of trialkyl phosphates using calorimetric and dielectric measurements over a wide temperature range. The results indicate a departure of the dielectric fragility indexes from the enthalpic ones as the length of the branch chain increases in the trialkyl phosphates. The Kirkwood correlation factor (g k ) is found to coincide at ∼0.6 at glass transition temperature (T g ) from triethyl phosphate to tributyl phosphate, indicating a similar structural alignment. The enthalpic relaxation serving as the more fundamental relaxation relevant to the structural relaxation is confirmed. Strikingly, we observed the relation of T g to the chain length in alkyl phosphates, revealing a minimum T g behavior, and its explanation assists in the understanding of the glass transition in relation to the structure of the glass-formers.

Direct Experimental Characterization of Contributions from Self-Motion of Hydrogen and from Interatomic Motion of Heavy Atoms to Protein Anharmonicity.

One fundamental challenge in biophysics is to understand the connection between protein dynamics and its function. Part of the difficulty arises from the fact that proteins often present local atomic motions and collective dynamics on the same time scales, and challenge the experimental identification and quantification of different dynamic modes. Here, by taking lyophilized proteins as the example, we combined deuteration technique and neutron scattering to separate and characterize the self-motion of hydrogen and the collective interatomic motion of heavy atoms (C, O, N) in proteins on the pico-to-nanosecond time scales. We found that hydrogen atoms present an instrument-resolution-dependent onset for anharmonic motions, which can be ascribed to the thermal activation of local side-group motions. However, the protein heavy atoms exhibit an instrument-resolution-independent anharmonicity around 200 K, which results from unfreezing of the relaxation of the protein structures on the laboratory equilibrium time (100-1000 s), softening of the entire bio-macromolecules.

Why is the change of the Johari-Goldstein ß-relaxation time by densification in ultrastable glass minor?

Ultrastable glasses (USG) formed by vapor deposition are considerably denser. The onset temperature of devitrification, Ton, is significantly higher than Ton or Tg of ordinary glass (OG) formed by cooling, which implies an increase of the structural α-relaxation time by many orders of magnitude in USG compared to that in OG at the same temperature. However, for a special type of secondary relaxation having properties strongly connected to those of the α-relaxation, called the Johari-Goldstein ß-relaxation, its relaxation time in USG is about an order of magnitude slower than that in OG and it has nearly the same activation energy, Eß. The much smaller change in τß and practically no change in Eß by densification in USG are in stark contrast to the behavior of the α-relaxation. This cannot be explained by asserting that the Johari-Goldstein (JG) ß-relaxation is insensitive to densification in USG, since the JG ß-relaxation strength is significantly reduced in USG to such a level that it would require several thousands of years of aging for an OG to reach the same state, and therefore the JG ß-relaxation does respond to densification in USG like the α-relaxation. Here, we provide an explanation based on two general properties established from the studies of glasses and liquids at elevated pressures and applied to USG. The increase in density of the glasses formed under high pressure can be even larger than that in USG. One property is the approximate invariance of the ratio τα(Ton)/τß(Ton) to density change at constant τα(Ton), and the other is the same ργ/T-dependence of τß in USG and OG where ρ is the density and γ is a material constant. These two properties are derived using the Coupling Model, giving a theoretical explanation of the phenomena. The explanation is also relevant for a full understanding of the experimental result that approximately the same surface diffusion coefficient is found in USG and OG with and without physical aging, and ultrathin films of a molecular glass-former.

Distinguishing different classes of secondary relaxations from vapour deposited ultrastable glasses.

Secondary relaxations persistent in the glassy state after structural arrest are especially relevant for the properties of the glass. A major thrust in research in dynamics of glass-forming liquids is to identify what secondary relaxations exhibit a connection to the structural relaxation and are hence more relevant. Via the Coupling Model, secondary relaxations having such connection have been identified by properties similar to the primitive relaxation of the Coupling Model and are called the Johari-Goldstein (JG) ß-relaxations. They involve the motion of the entire molecule and act as the precursor of the structural α-relaxation. The change in dynamics of the secondary relaxation by aging an ordinary glass is one way to understand the connection between the two relaxations, but the results are often equivocal. Ultrastable glasses, formed by physical vapour deposition, exhibit density and enthalpy levels comparable to ordinary glasses aged for thousands of years, as well as some particular molecular arrangement. Thus, ultrastable glasses enable the monitoring of the evolution of secondary processes in case aging does not provide any definitive information. Here, we study the secondary relaxation of several ultrastable glasses to identify different types of secondary relaxations from their different relationship with the structural relaxation. We show the existence of two clearly differentiated groups of relaxations: those becoming slower in the ultrastable state and those becoming faster, with respect to the ordinary unaged glass. We propose ultrastability as a way to distinguish between secondary processes arising from the particular microstructure of the system and those connected in properties to and acting as the precursor of the structural relaxation in the sense of the Coupling Model.

Molecular dynamics, physical and thermal stability of neat amorphous amlodipine besylate and in binary mixture.

In this paper, a stable amorphous solid dispersion of an antihypertensive drug, amlodipine besylate (AMB) was prepared by entrapping it in a polymer matrix, polyvinyl pyrrollidone, in different weight ratios (AMB/PVP 05:95, 10:90, 20:80, 30:70). The glass forming ability of all binary dispersions were studied by means of differential scanning calorimetry and found good correlation between experimental Tg and Fox Flory's prediction. By considering the daily dosage limit of 5 mg, a weight ratio of 05:95 was further considered for the study. The structures of neat and binary of AMB were characterized by density functional theory, Fourier transform infrared spectroscopy, Fourier transform Raman spectroscopy and UV-visible spectroscopy. Further, detailed molecular dynamics of both pure and binary were investigated using broadband dielectric spectroscopy to judge the physical stability of the amorphous dispersions. Translation-rotation coupling of AMB possibly explains the dual conductivity and dipolar nature of the secondary relaxation in neat AMB. Thus, the binary dispersion of AMB with commercially acceptable weight ratio with strong glass forming behaviour and better shelf life was prepared and characterized for practical applications.