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Broadband dielectric spectroscopy and pressure-temperature-volume methods are employed to investigate the effect of hydrostatic pressure on the conductivity relaxation time (τσ), both in the supercooled and glassy states of protic ionic liquid lidocaine hydrochloride monohydrate. Due to the decoupling between the ion conductivity and structural dynamics, the characteristic change in behavior of τσ(T) dependence, i.e., from Vogel-Fulcher-Tammann-like to Arrhenius-like behavior, is observed. This crossover is a manifestation of the liquid-glass transition of lidocaine HCl. The similar pattern of behavior was also found for pressure dependent isothermal measurements. However, in this case the transition from one simple volume activated law to another was noticed. Additionally, by analyzing the changes of conductivity relaxation times during isothermal densification of the sample, it was found that compression enhances the decoupling of electrical conductivity from the structural relaxation. Herein, we propose a new parameter, dlogRτ/dP, to quantify the pressure sensitivity of the decoupling phenomenon. Finally, the temperature and volume dependence of τσ is discussed in terms of thermodynamic scaling concept. [ABSTRACT FROM AUTHOR]

In this paper, we investigate the effect of pressure on the molecular dynamics of protic ionic liquid lidocaine hydrochloride, a commonly used pharmaceutical, by means of dielectric spectroscopy and pressure-temperature-volume methods. We observed that near Tg the pressure dependence of conductivity relaxation times reveals a peculiar behavior, which can be treated as a manifestation of decoupling between ion migration and structural relaxation times. Moreover, we discuss the validity of thermodynamic scaling in lidocaine HCl. We also employed the temperature-volume Avramov model to determine the value of pressure coefficient of glass transition temperature, dTg/dP|P = 0.1. Finally, we investigate the role of thermal and density fluctuations in controlling of molecular dynamics of the examined compound. [ABSTRACT FROM AUTHOR]

Broadband dielectric measurements on leucrose were performed under ambient and high pressure. We showed that in this disaccharide, there are two secondary relaxation modes, a slower one sensitive to pressure and a faster one that is not. This finding clearly indicates that the faster secondary relaxation originates from the intramolecular motion. This conclusion contradicted previous interpretations of this mode observed for trehalose and maltitol, systems very closely related to leucrose. In addition, pressure sensitivity of the slower relaxation confirms our recent interpretation about the character of this process. Furthermore, we discovered that unlike the faster relaxation, the slower secondary relaxation is sensitive to the thermodynamic history of measurements. Finally, monitoring the changes in maximum loss of the slower secondary relaxation measured at the same pressure and temperature conditions for glasses obtained via different thermodynamic routes enabled us to draw a conclusion about the density of the formed glasses. Our observations may be helpful in establishing a new method of suppressing crystallization of amorphous drugs. [ABSTRACT FROM AUTHOR]

The slow secondary (β) process of 1,1′-bis (4-methoxyphenyl) cyclohexane and phenolphthalein dimethylether has been investigated by dielectric spectroscopy. New experimental results about the pressure dependence of the two processes are reported, as well as new data about the dependence of the characteristic relaxation frequency on the cooling rate used to vitrify the system in isobaric conditions. Previous investigations on these systems suggested that the first one is not a true Johari-Goldstein relaxation and both processes should originate from the flip flop motion of the phenyl ring. The results herein reported evidence that the characteristic frequency of the β process of phenolphthalein dimethylether is more sensitive to pressure variation and to the vitrification procedure than that of 1,1′-bis (4-methoxyphenyl) cyclohexane. Such results suggest an intermolecular origin for the secondary process in phenolphthalein dimethylether and an intramolecular origin for the other one, which do not completely agree with the previous interpretation. We evidence that the microscopic mechanism at the basis of these two processes is still an open question, which should be debated on the basis of new experimental investigations. [ABSTRACT FROM AUTHOR]

Broadband dielectric measurements for anhydrous tripropylene glycol (3PG) and 96, 92, 84, 80, 74, 71, and 68 wt % 3PG-water mixtures are performed in the frequency range of 10-2–107 Hz and in the temperature range of 123–243 K. We examined the effect of adding water into anhydrous 3PG on relaxation dynamics. Apart from the two well-known relaxation processes, i.e., α and β for anhydrous 3PG we observed new relaxation peak (β′) for all aqueous mixtures of 3PG. In addition we found the critical mole fraction of water xw=0.67 in which relaxation dynamics changes its behavior. According to the Sudo approach [S. Sudo et al., J. Non-Cryst. Solids 307–310, 356 (2002)], the behavior of relaxation processes was interpreted assuming the existence of three kinds of cooperative domains (CDs): containing only 3PG molecules, including only water molecules, and including both 3PG and water molecules, which molecules of each kind CD are bound by hydrogen bonds. [ABSTRACT FROM AUTHOR]

Broadband dielectric measurements were carried out at isobaric and isothermal conditions up to 1.75 GPa for reconsidering the relaxation dynamics of decahydroisoquinoline, previously investigated by Richert et al. [R. Richert, K. Duvvuri, and L.-T. Duong, J. Chem. Phys. 118, 1828 (2003)] at atmospheric pressure. The relaxation time of the intense secondary relaxation τβ seems to be insensitive to applied pressure, contrary to the α-relaxation times τα. Moreover, the separation of the α- and β-relaxation times lacks correlation between shapes of the α-process and β-relaxation times, predicted by the coupling model [see for example, K. L. Ngai, J. Phys.: Condens. Matter 15, S1107 (2003)], suggesting that the β process is not a true Johari–Goldstein (JG) relaxation. From the other side, by performing measurements under favorable conditions, we are able to reveal a new secondary relaxation process, otherwise suppressed by the intense β process, and to determine the temperature dependence of its relaxation times, which is in agreement with that of the JG relaxation. [ABSTRACT FROM AUTHOR]

The dielectric spectrum of the organic glass former 1,1'-bis (p-methoxyphenyl) cyclohexane was measured over a range of temperatures and pressures, corresponding to a variation of the structural relaxation time, Τα, by 8 decades. The temperature dependence of Τ[sub α] corresponded to a fragility equal to 72, which is consistent with the correlation of same with the shape (breadth) of the relaxation function. The dependence on pressure of Τ[sub α] could be described as a simple activated process, with a pressure-independent activation volume equal to ∼230 cm³/mol, varying inversely with temperature. The pressure coefficient of the glass temperature, T[sub g], was 240 K/GPa. At frequencies beyond the structural relaxation peak, there is a second, thermally activated process, having an activation energy=74.2 kJ/mol. The relaxation times for this process were invariant to pressure. Extrapolation of these relaxation times (measured below the T[sub g]) intersects the ambient pressure structural relaxation data at a temperature, T[sub β]=268 K. This is about equal to the temperature, T[sub B], at which the structural relaxation times deviated from a single Vogel-FulcherTamman curve. In this respect, the secondary process exhibits the properties of a Johari-Goldstein relaxation. However, since T[sub β] varies with pressure, it remains to be seen whether its equivalence to T[sub B] is maintained at elevated pressure. [ABSTRACT FROM AUTHOR]

The effect of pressure on the dielectric relaxation of two polyhydroxy alcohols is examined by analysis of existing data on glycerol, together with new measurements on xylitol. The fragility, or T[sub g]-normalized temperature dependence, changes with pressure for low pressures, but becomes invariant above 1 GPa. When compared at temperatures for which the α-relaxation times are equal, there is no effect of pressure (< 1 GPa) on the shape of the α dispersion at higher temperatures. However, nearer T[sub g], pressure broadens the a peak, consistent with the expected correlation of fragility with the breadth of the relaxation function. We also observe that the α-relaxation peaks for both glycerol and xylitol show an excess intensity at higher frequencies. For xylitol, unlike for glycerol, at lower temperatures this wing disjoins to form a separate peak. For both glass formers, elevated pressure causes the excess wing to become more separated from the peak maximum; that is, the properties of the primary and excess intensities are not correlated. This implies that the excess wing in glycerol is also a distinct secondary process, although it cannot be resolved from the primary peak. [ABSTRACT FROM AUTHOR]

Several studies are conducted to explain the different molecular motions that are found to be responsible for the slower secondary ([beta]) relaxation in sucrose. The [beta]-relaxation is shown to lead to the translation motion of the entire molecule of the sugar.

The effect of molecular structure on the dynamical properties of supercooled di-n-butyl phthalate (DBP) and its isomer, diisobutyl phthalate (DiBP) is examined. The results of the dielectric alpha- and beta-relaxations and the ionic conductivity are discussed.

Looks into the effect of pressure on fragility and glass transition temperature in fragile glass-former. Temperature dependences of dielectric relaxation times measured for several different pressures; Findings of the strong fragility analyses carried out for dielectric data; Influence of pressure on glass transition temperature.

The aim of this work is to analyze in detail the effect of the alkyl chain length on the dynamics of glass-forming propylene carbonate (PC) derivatives. Examined samples are low-molecular weight derivatives of the PC structure, i.e., the 4-alkyl-1,3-dioxolan-2-one series, modified by changing the alkyl substituent from methyl to hexyl. The molecular dynamics (MD) has been analyzed based on experimental data collected from differential scanning calorimetry, broadband dielectric spectroscopy (BDS), X-ray diffraction (XRD), and nuclear magnetic resonance relaxometry measurements as well as MD simulations. The dielectric results show in samples with the propyl- or longer carbon chain the presence of slow Debye-like relaxation with features similar to those found in associative materials. Both XRD and MD reveal differences in the intermolecular structure between PC and 4-butyl-1,3-dioxolan-2-one liquids. Moreover, MD shows that the probability of finding one terminal carbon atom of the side chain of BPC in the vicinity of another carbon atom of the same type is much higher than in the case of PC. It suggests that there is a preference for longer hydrocarbon chains to set themselves close to each other. Consequently, the observed slow-mode peak may be caused by movement of aggregates maintained by van der Waals interactions. Reported herein, findings provide a new insight into the molecular origin of Debye-like relaxation.

Electrical conductivity of the supercooled ionic liquid [C8MIM][NTf2], determined as a function of temperature and pressure, highlights strong differences in its ionic transport behavior between low and high temperature regions. To date, the crossover effect which is very well known for low molecular van der Waals liquids has been rarely described for classical ionic liquids. This finding highlights that the thermal fluctuations could be dominant mechanisms driving the dramatic slowing down of ion motions near Tg. An alternative way to analyze separately low and high temperature dc-conductivity data using a density scaling approach was then proposed. Based on which a common value of the scaling exponent γ = 2.4 was obtained, indicating that the applied density scaling is insensitive to the crossover effect. By comparing the scaling exponent γ reported herein along with literature data for other ionic liquids, it appears that γ decreases by increasing the alkyl chain length on the 1-alkyl-3-methylimidazolium-based ionic liquids. This observation may be related to changes in the interaction between ions in solution driven by an increase in the van der Waals type interaction by increasing the alkyl chain length on the cation. This effect may be related to changes in the ionic liquid nanostructural organization with the alkyl chain length on the cation as previously reported in the literature based on molecular dynamic simulations. In other words, the calculated scaling exponent γ may be then used as a key parameter to probe the interaction and/or self-organizational changes in solution with respect to the ionic liquid structure.

Ionic systems with enhanced proton conductivity are widely viewed as promising electrolytes in fuel cells and batteries. Nevertheless, a major challenge toward their commercial applications is determination of the factors controlling the fast proton hopping in anhydrous conditions. To address this issue, we have studied novel proton-conducting materials formed via a chemical reaction of lidocaine base with a series of acids characterized by a various number of proton-active sites. From ambient and high pressure experimental data, we have found that there are fundamental differences in the conducting properties of the examined salts. On the other hand, DFT calculations revealed that the internal proton hopping within the cation structure strongly affects the pathways of mobility of the charge carrier. These findings offer a fresh look on the Grotthuss-type mechanism in protic ionic glasses as well as provide new ideas for the design of anhydrous materials with exceptionally high proton conductivity.

By using the dielectric relaxation method, we studied molecular dynamics of α-tetralone. Our purpose was to reveal the molecular origin of secondary processes observed for this very simple-structured molecule. To this end, we carried out dielectric measurements at both ambient and elevated pressure of neat α-tetralone and in mixture with oligostyrene. By means of both experimental observations and theoretical calculations, we proved that one of the secondary relaxations has the intramolecular origin, while the other is undoubtedly the intermolecular process called Johari-Goldstein relaxation characteristic of the glassy state.

New dielectric spectroscopy results are reported for propylene carbonate (PC), glycerol, and threitol, measured at very high (1.8 GPa) pressure. These glass formers all exhibit an excess wing in their dielectric spectrum above T(g). We show that the shape of the alpha peak and excess wing of PC are invariant to pressure and temperature, when compared at a fixed value of the alpha -relaxation time. However, for the hydrogen-bonded liquids, there is a marked breakdown of this temperature-pressure superpositioning, due to a change in chemical structure (i.e., concentration of hydrogen bonds) with change of temperature or pressure. For all these materials, we can conclude that the excess wing is merely a secondary relaxation, masked under ordinary conditions by the intense, overlapping alpha peak.

The effect of pressure variation on dynamics of alpha relaxation process in poly[(phenyl glycidyl ether)-co-formaldehyde] has been investigated both under isothermal (T=293 K) and isobaric (P=0.1, 60, 120, 180, and 240 MPa) conditions using broad band dielectric spectroscopy (10(-2) to 10(6) Hz). The alpha relaxation is analyzed by means of the Havriliak-Negami relaxation function which has two shape parameters (alpha and gamma) to characterize non-Debye behavior. As a result we found that the shape parameters of the dielectric function collected for different pressures fall on master curves constructed by plotting alpha and alphagamma against the logarithm of relaxation time. The scaling of shape parameters for different pressure stems from pressure independence of fragility. This provides strong experimental evidence supporting correlation of non-Debye behavior with non-Arrhenius relaxation under high pressure. From an analysis of the shape parameters of relaxation function, in terms of the Schonhals and Schlosser model, we drew conclusions that the molecular mobility of PPG is controlled in the same way by temperature and pressure. The relaxation times exhibit a clear non-Arrhenius behavior under isothermal and isobaric condition.