Biomedical subjects

K L Ngai

Publications and source records attributed to K L Ngai.

At least 19 recordsLinked to original sources

PubMed2006

On enhanced translational diffusion or the fractional Stokes-Einstein relation observed in a supercooled ionic liquid.

From their experimental studies of the supercooled molecular ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate (BMIM-HFP), Ito and Richert [J. Phys. Chem. B 2006, in press.] found that the Stokes-Einstein and the Debye-Stokes-Einstein laws do not hold. Instead, enhanced translational diffusion or fractional Stokes-Einstein and fractional Debye-Stokes-Einstein relations are observed, just like in nonionic glass-forming liquids, including 1,3-bis(1-naphthyl)-5-(2-naphthyl)benzene, o-terphenyl, and sucrose benzoate. The comprehensive measurements made by Ito and Richert have determined the critical parameters that the coupling model needs to explain the observed fractional Stokes-Einstein and fractional Debye-Stokes-Einstein relations in the supercooled molecular ionic liquid.

Journal Article↗

PubMed2006

The true Johari-Goldstein beta-relaxation of monosaccharides.

Broadband isothermal dielectric relaxation measurements of anhydrous fructose, glucose, galactose, sorbose, and ribose were made at ambient pressure in their liquidus and glassy states. We found a new secondary relaxation in fructose and glucose that is slower than those seen before by others. This new secondary relaxation also appears in the dielectric spectra of galactose, sorbose, and ribose, and hence it is a general feature of the relaxation dynamics of the monosaccharides. Dielectric measurements at elevated pressure of fructose and ribose show that the new secondary relaxation shifts to lower frequencies with applied pressures, mimicking the behavior of the alpha-relaxation. In contrast, the faster secondary relaxation remains stationary on applying pressure. These results together with other inferences indicate that the slower secondary relaxation bears relations to the alpha-relaxation, and hence, it is the true Johari-Goldstein secondary relaxation of the monosaccharides.

Molecular Structure↗

PubMed2006

Changes of relaxation dynamics of a hydrogen-bonded glass former after removal of the hydrogen bonds.

Dielectric relaxation spectra of two closely related glass formers, dipropylene glycol [H-(C3H6O)2-OH] and dipropylene glycol dimethyl ether [CH3-O-(C3H6O)2-CH3], were measured at ambient and elevated pressures in the supercooled and the glassy states are presented. Hydrogen bonds formed in dipropylene glycol are removed when its ends are replaced by two methyl groups to become dipropylene glycol dimethyl ether. In the process, the primary relaxation, the excess wing, and the resolved secondary relaxation of dipropylene glycol are all modified when the structure is transformed to become dipropylene glycol dimethyl ether. The modifications include the pressure and temperature dependences of these relaxation processes and their interrelations. Thus, by comparing the dielectric spectra of these two closely related glass formers at ambient and elevated pressures, the differences in the relaxation dynamics and properties in the presence and absence of hydrogen bonding are identified.

Journal Article↗

PubMed2006

Primary and secondary relaxations in supercooled eugenol and isoeugenol at ambient and elevated pressures: dependence on chemical microstructure.

Dielectric loss spectra of two glass-forming isomers, eugenol and isoeugenol, measured at ambient and elevated pressures in the normal liquid, supercooled, and glassy states are presented. The isomeric chemical compounds studied differ only by the location of the double bond in the alkyl chain. Above the glass transition temperature T(g), the dielectric loss spectra of both isomers exhibit an excess wing on the high frequency flank of the loss peak of the alpha relaxation and an additional faster gamma process at the megahertz frequency range. By decreasing temperature below T(g) at ambient pressure or by elevating pressure above P(g), the glass transition pressure, at constant temperature, the excess wing of isoeugenol shifts to lower frequencies and is transformed into a secondary beta-loss peak, while in eugenol it becomes a shoulder. These spectral features enable the beta-relaxation time tau(beta) to be determined in the glassy state. These changes indicate that the excess wings in isoeugenol and eugenol are similar and both are secondary beta relaxations that are not resolved in the liquid state. While in both isoeugenol and eugenol the loss peak of the beta relaxation in the glassy state and the corresponding excess wing in the liquid state shifts to lower frequencies on elevating pressure, the locations of their gamma relaxation show little change with increasing pressure. The different pressure sensitivities of the excess wing and gamma relaxation are further demonstrated by the nearly perfect superposition of the alpha-loss peak together with excess wing from the data taken at ambient pressure and at elevated pressure (and higher temperature so as to have the same alpha-peak frequency), but not the gamma-loss peak in both isoeugenol and eugenol. On physical aging isoeugenol, the beta-loss peak shifts to lower frequencies, but not the gamma relaxation. Basing on these experimental facts, the faster gamma relaxation is a local intramolecular process involving a side group and the slower beta relaxation mimics the structural alpha relaxation in behavior, involves the entire molecule and satisfies the criteria for being the Johari-Goldstein beta relaxation. Analysis and interpretation of the spectra utilizing the coupling model further demonstrate that the excess wings seen in the equilibrium liquid states of these two isomers are their genuine Johari-Goldstein beta relaxation.

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PubMed2006

Anomalous narrowing of the structural relaxation dispersion of tris(dimethylsiloxy)phenylsilane at elevated pressures.

Broadband dielectric relaxation measurements of tris(dimethylsiloxy)phenylsilane were made at ambient pressure and at elevated pressures. The data show an anomalous behavior not previously seen in any other glass-formers; namely, the structural alpha-relaxation loss peak narrows with increasing pressure and temperature at constant peak frequency. Interpreted by the coupling model, the effect is due to reduction of intermolecular coupling at elevated pressures. This interpretation has support from the observed decrease of the separation between the alpha-relaxation and the Johari-Goldstein secondary relaxation, as well as the smaller steepness or "fragility" index m of the data obtained at 1.7 GPa than at ambient pressure.

Journal Article↗

PubMed2005

Primary and secondary relaxations in bis-5-hydroxypentylphthalate revisited.

The molecular structure of bis-5-hydroxypentylphthalate (BHPP) is like dihexyl phthalate but having appended to it two hydroxyl end groups, which contribute additional dipole moments and capacity for hydrogen-bond formation. In a previously published dielectric study of the primary and secondary relaxations of BHPP, it was found that all the dynamic properties are normal except for the anomalously large width of the primary relaxation loss peak. There are two secondary relaxations, the relaxation time of the slower one increases with increasing pressure, whereas that of the faster one is practically insensitive to pressure. Hence, the slower secondary relaxation is the "universal" Johari-Goldstein (JG) [J. Chem. Phys. 53, 2372 (1970); 55, 4245 (1971)] relaxation in BHPP. All is well except if the observed large width of the primary relaxation were an indication of a corresponding large coupling parameter n=0.45 in the coupling model. Then the predicted relations between the primary relaxation time tau(alpha) and the JG relaxation time tau(JG) found previously to hold in many glass formers would be violated. It was recognized that this singular behavior of BHPP is likely due to broadening of the primary loss peak by the overlapping contributions of two independent dipole moments present in BHPP, and the actual coupling parameter is smaller. However, at the time of publication of the previous work there were not enough data to support this explanation. By making broadband dielectric measurements of dibutyl phthalate (DBP) and dioctyl phthalate (DOP) that have chemical structures closely related to BHPP but with only one dipole moment, we show that all their dynamic properties are almost the same as BHPP but the widths of their primary relaxation loss peaks are significantly narrower corresponding to a smaller coupling parameter n=0.34. The new data presented here indicate that the coupling parameter of BHPP is about the same as DBP and DOP, and the predicted relations between tau(alpha) and tau(JG) of BHPP are brought back in agreement with the experimental data.

Journal Article↗

PubMed2005

Do theories of the glass transition, in which the structural relaxation time does not define the dispersion of the structural relaxation, need revision?

Upon decreasing temperature or increasing pressure, a noncrystallizing liquid will vitrify; that is, the structural relaxation time, taualpha, becomes so long that the system cannot attain an equilibrium configuration in the available time. Theories, including the well-known free volume and configurational entropy models, explain the glass transition by invoking a single quantity that governs the structural relaxation time. The dispersion of the structural relaxation (i.e., the structural relaxation function) is either not addressed or is derived as a parallel consequence (or afterthought) and thus is independent of taualpha. In these models the time dependence of the relaxation bears no fundamental relationship to the value of taualpha or other dynamic properties. Such approaches appear to be incompatible with a general experimental fact recently discovered in glass-formers: for a given material at a fixed value of taualpha, the dispersion is constant, independent of thermodynamic conditions (T and P); that is, the shape of the alpha-relaxation function depends only on the relaxation time. If derived independently of taualpha, it is an unlikely result that the dispersion of the structural relaxation would be uniquely defined by taualpha.

Journal Article↗

PubMed2005

Emergence of the genuine Johari-Goldstein secondary relaxation in m-fluoroaniline after suppression of hydrogen-bond-induced clusters by elevating temperature and pressure.

The dielectric spectra of the glass former, m-fluoroaniline (m-FA), at ambient pressure show the presence of a secondary relaxation, which was identified in the literature as the universal Johari-Goldstein (JG) beta relaxation. However, published elastic neutron scattering and simulation data [D. Morineau, C. Alba-Simionesco, M. C. Bellisent-Funel, and M. F. Lauthie, Europhys. Lett. 43, 195 (1998); D. Morineau and C. Alba-Simionesco, J. Chem. Phys. 109, 8494 (1998)] showed the presence of hydrogen-bond-induced clusters of limited size in m-FA at ambient pressure and temperature of the dielectric measurements. The observed secondary relaxation may originate from the hydrogen-bond-induced clusters. If so, it should not be identified with the JG beta relaxation that involves essentially all parts of the molecule and has certain characteristics [K. L. Ngai and M. Paluch, J. Chem. Phys. 120, 857 (2004)], but then arises the question of where is the supposedly universal JG beta relaxation in m-FA. To gain a better understanding and resolving the problem, we perform dielectric measurements at elevated pressures and temperatures to suppress the hydrogen-bond-induced clusters and find significant changes in the dielectric spectra. The secondary relaxation observed at ambient pressure in m-FA is suppressed, indicating that indeed it originates from the hydrogen-bond-induced clusters. The spectra of m-FA are transformed at high temperature and pressure to become similar to that of toluene. The new secondary relaxation that emerges in the spectra has properties of a genuine JG relaxation like in toluene.

Journal Article↗

PubMed2005

Two secondary modes in decahydroisoquinoline: which one is the true Johari Goldstein process?

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 tau(beta) seems to be insensitive to applied pressure, contrary to the alpha-relaxation times tau(alpha). Moreover, the separation of the alpha- and beta-relaxation times lacks correlation between shapes of the alpha-process and beta-relaxation times, predicted by the coupling model [see for example, K. L. Ngai, J. Phys.: Condens. Matter 15, S1107 (2003)], suggesting that the beta 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 beta process, and to determine the temperature dependence of its relaxation times, which is in agreement with that of the JG relaxation.

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PubMed2005

Breather-induced anomalous charge diffusion.

We present results on the diffusive motion of a charge interacting with the nonlinear dynamics of a thermalized underlying lattice. Signatures of anomalous diffusive properties are found at relatively high temperatures, where highly nonlinear excitations are present. A sublinear diffusion and a plateau appear before the standard long-time diffusion during the evolution of the mean-squared displacement and a significant degree of heterogeneity is exhibited among individual trajectories. Both properties are connected with the existence of vibrational hot spots (breather or multibreather excitations). Transport parameters of the charge are strongly affected in this case, as can be exemplified by the significant suppression of the diffusion coefficient D. The variation of D with temperature follows a stretched exponential law. The results are contrasted with those of the linearized case, in the absence of breathers. Such anomalous diffusion of a charge coupled to a thermalized lattice may be relevant in low-dimensional soft materials with strong anharmonicities, such as biomolecules, conducting polymers, etc.

Biopolymers↗

PubMed2005

Multifractal analysis of dynamic potential surface of ion-conducting materials.

A multifractal analysis using singularity spectra [T.C. Halsey et al., Phys. Rev. A 33, 1141 (1986)] provides a general tool to study the temporal-spatial properties of particles in complex disordered materials such as ions in ionically conducting glasses and melts. Obtained by molecular-dynamics simulations, the accumulated positions of the particles dynamically form a structural pattern called the dynamical potential surface. In this work, the complex dynamical potential surfaces of Li ions in the lithium silicates were visualized and characterized by the multifractal analysis. The fractal dimensions and strength of the singularity related to the spatial intermittency of the dynamics are examined, and the relationship between dynamics and the singularity spectra is discussed.

Journal Article↗

PubMed2005

Relation between the alpha-relaxation and Johari-Goldstein beta-relaxation of a component in binary miscible mixtures of glass-formers.

The coupling model was applied to describe the alpha-relaxation dynamics of each component in perfectly miscible mixtures A(1-x)B(x) of two different glass-formers A and B. An important element of the model is the change of the coupling parameter of each component with the composition, x, of the mixture. However, this change cannot be determined directly from the frequency dispersion of the alpha-relaxation of each component because of the broadening caused by concentration fluctuations in the mixture, except in the limits of low concentrations of either component, x --> 0 and x --> 1. Fortunately, the coupling model has another prediction. The coupling parameter of a component, say A, in the mixture determines tau(alpha)/tau(JG), the ratio of the alpha-relaxation time, tau(alpha), to the Johari-Goldstein (JG) secondary relaxation time, tau(JG), of the same component A. This prediction enables us to obtain the coupling parameter, n(A), of component A from the isothermal frequency spectrum of the mixture that shows both the alpha-relaxation and the JG beta-relaxation of component A. We put this extra prediction into practice by calculating n(A) of 2-picoline in binary mixtures with either tri-styrene or o-terphenyl from recently published broadband dielectric relaxation data of the alpha-relaxation and the JG beta-relaxation of 2-picoline. The results of n(A) obtained from the experimental data show its change with composition, x, follows the same pattern as assumed in previous works that address only the alpha-relaxation dynamics of a component in binary mixtures based on the coupling model. There is an alternative view of the thrust of the present work. If the change of n(A) with composition, x, in considering the alpha-relaxation of component A is justified by other means, the theoretical part of the present work gives a prediction of how the ratio tau(alpha)/tau(JG) of component A changes with composition, x. The data of tau(alpha) and tau(JG) of 2-picoline mixed with tri-styrene or o-terphenyl provide experimental support for the prediction.

Journal Article↗

PubMed2005

Time series analysis of ion dynamics in glassy ionic conductors obtained by a molecular dynamics simulation.

We present several characteristics of ionic motion in glassy ionic conductors brought out by time series analysis of molecular dynamics (MD) simulation data. Time series analysis of data obtained by MD simulation can provide crucial information to describe, understand and predict the dynamics in many systems. The data have been treated by the singular spectrum analysis (SSA), which is a method to extract information from noisy short time series and thus provide insight into the unknown or partially unknown dynamics of the underlying system that generated the time series. Phase-space plot reconstructed using the principal components of SSA exhibited complex but clear structures, suggesting the deterministic nature of the dynamics.

Journal Article↗

PubMed2004

Comment on "Origin of the excess wing and slow beta relaxation of glass formers: a unified picture of local orientational fluctuations".

In a recent paper [Phys. Rev. E 69, 021502 (2004)]], Tanaka commented on an old coupling model interpretation of the Johari-Goldstein (JG) secondary relaxation [J. Chem. Phys. 115, 1405 (2001)]]; namely, that it implies not all molecules contribute to the JG relaxation. In this Comment, I point out to the readers that this old interpretation has been revised in recent publications [J. Phys.: Condens. Matter 15, S1107 (2003)]; J. Phys. Chem. B 107, 6865 (2003)]; J. Chem. Phys. 120, 857 (2004)]; Macromolecules 37, 8123 (2004)]]. In the new interpretation, essentially all molecules contribute to the JG relaxation. Another comment of Tanaka that applies to both the old and the new interpretation is discussed and shown to be of no practical significance.

Comment↗

PubMed2004

Does the interaction potential determine both the fragility of a liquid and the vibrational properties of its glassy state?

By performing molecular dynamics simulations of binary Lennard-Jones systems with three different potentials, we show that the increase of anharmonicity and capacity for intermolecular coupling of the potential is the cause of (i) the increase of kinetic fragility and nonexponentiality in the liquid state, and (ii) the T(g)-scaled temperature dependence of the nonergodicity parameter determined by the vibrations at low temperatures in the glassy state. Naturally, these parameters correlate with each other, as observed experimentally by T. Scopigno et al. [Science 302, 849 (2003)]

Journal Article↗

PubMed2004

Effects of water on the primary and secondary relaxation of xylitol and sorbitol: implication on the origin of the Johari-Goldstein relaxation.

Dielectric spectroscopy was employed to study the effects of water on the primary alpha -relaxation and the secondary beta -relaxation of xylitol. The measurements were made on anhydrous xylitol and mixtures of xylitol with water with three different water concentrations over a temperature range from 173 K to 293 K. The alpha -relaxation speeds up with increasing concentration of water in xylitol, whereas the rate of the beta -relaxation is essentially unchanged. Some systematic differences in the behavior of alpha -relaxation for anhydrous xylitol and the mixtures were observed. Our findings confirm all the observations of Nozaki et al. [J. Non-Cryst. Solids 307, 349 (2002)]] in sorbitol/water mixtures. Effects of water on both the alpha - and beta -relaxation dynamics in xylitol and sorbitol are explained by using the coupling model.

Journal Article↗

PubMed2004

"Cooperativity blockage" in the mixed alkali effect as revealed by molecular-dynamics simulations of alkali metasilicate glass.

The relaxation dynamics of a complex interacting system can be drastically changed when mixing with another component having different dynamics. In this work, we elucidate the effect of the less mobile guest ions on the dynamics of the more mobile host ions in mixed alkali glasses by molecular-dynamics (MD) simulations. One MD simulation was carried out on lithium metasilicate glass with the guest ions created by freezing some randomly chosen lithium ions at their initial locations at 700 K. A remarkable slowing down of the dynamics of the majority mobile Li ions was observed both in the self-part of the density-density correlation function, Fs(k,t), and in the mean-squared displacements. On the other hand, there is no significant change in the structure. The motion of the Li ions in the unadulterated Li metasilicate glass is dynamically heterogeneous. In the present work, the fast and slow ions were divided into two groups. The number of fast ions, which shows faster dynamics (Levy flight) facilitated by cooperative jumps, decreases considerably when small amount of Li ions are frozen. Consequently there is a large overall reduction of the mobility of the Li ions. The result is also in accordance with the experimental finding in mixed alkali silicate glasses that the most dramatic reduction of ionic conductivity occurs in the dilute foreign alkali limit. Similar suppression of the cooperative jumps is observed in the MD simulation data of mixed alkali system, LiKSiO3. Naturally, the effect found here is appropriately described as "cooperativity blockage." Slowing down of the motion of Li ions also was observed when a small number of oxygen atoms chosen at random were frozen. The effect is smaller than the case of freezing some the Li ions, but it is not negligible. The cooperativity blockage is also implemented by confining the Li metasilicate glass inside two parallel walls formed by freezing Li ions in the same metasilicate glass. Molecular-dynamics simulations were performed on the dynamics of the Li ions in the confined glass. Slowing down of the dynamics is largest near the wall and decreases monotonically with distance away from the wall.

Journal Article↗

PubMed2004

Dynamics of caged ions in glassy ionic conductors.

At sufficiently high frequency and low temperature, the dielectric responses of glassy, crystalline, and molten ionic conductors all invariably exhibit nearly constant loss. This ubiquitous characteristic occurs in the short-time regime when the ions are still caged, indicating that it could be a determining factor of the mobility of the ions in conduction at longer times. An improved understanding of its origin should benefit the research of ion conducting materials for portable energy source as well as the resolution of the fundamental problem of the dynamics of ions. We perform molecular dynamics simulations of glassy lithium metasilicate (Li2SiO3) and find that the length scales of the caged Li+ ions motions are distributed according to a Levy distribution that has a long tail. These results suggest that the nearly constant loss originates from "dynamic anharmonicity" experienced by the moving but caged Li+ ions and provided by the surrounding matrix atoms executing correlated movements. The results pave the way for rigorous treatments of caged ion dynamics by nonlinear Hamiltonian dynamics.

Journal Article↗