Rotational correlation and dynamic heterogeneity in a kinetically constrained lattice gas

We study the dynamical heterogeneity and glassy dynamics in a kinetically constrained lattice-gas model which has both translational and rotational degrees of freedom. We find that the rotational relaxation time tracks the structural relaxation time as density is increased whereas the translational diffusion constant exhibits a strong decoupling. We investigate distributions of exchange and persistence times for both the rotational and translational degrees of freedom and compare our results on the distributions of rotational exchange times to recent single molecule studies.     

Molecular dynamics with quantum transitions study of the vibrational relaxation of the HOD bend fundamental in liquid D2O

The molecular dynamics with quantum transitions method is used to study the vibrational relaxation of the HOD bend fundamental in liquid D(2)O. All of the vibrational bending degrees of freedom of the HOD and D(2)O molecules are described by quantum mechanics, while the remaining translational and rotational degrees of freedom are described classically. The effect of the coupling between the rotational and vibrational degrees of freedom of the deuterated water molecules is analyzed. A kinetic mechanism based on three steps is proposed in order to interpret the dynamics of the system. It is shown that intermolecular vibrational energy transfer plays an important role in the relaxation process and also that the transfer of energy into the rotational degrees of freedom is favored over the transfer of energy into the translational motions. The thermalization of the system after the relaxation is reached in a shorter time scale than that of the recovery of the hydrogen bond network. The relaxation and equilibration times obtained compare well with experimental and previous theoretical results.     

Aging in a free-energy landscape model for glassy relaxation

The aging properties of a simple free-energy landscape model for the primary relaxation in supercooled liquids are investigated. The intermediate scattering function and the rotational correlation functions are calculated for the generic situation of a quench from a high temperature to below the glass transition temperature. It is found that the reequilibration of molecular orientations takes longer than for translational degrees of freedom. The time scale for reequilibration is determined by that of the primary relaxation as an intrinsic property of the model.     

Relaxation scenarios in a mixture of large and small spheres: dependence on the size disparity

We present a computational investigation on the slow dynamics of a mixture of large and small soft spheres. By varying the size disparity at a moderate fixed composition different relaxation scenarios are observed for the small particles. For small disparity density-density correlators exhibit moderate stretching. Only small quantitative differences are observed between dynamic features for large and small particles. On the contrary, large disparity induces a clear time scale separation between the large and small particles. Density-density correlators for the small particles become extremely stretched and display logarithmic relaxation by properly tuning the temperature or the wave vector. Self-correlators decay much faster than density-density correlators. For very large size disparity, a complete separation between self- and collective dynamics is observed for the small particles. Self-correlators decay to zero at temperatures where density-density correlations are frozen. The dynamic picture obtained by varying the size disparity resembles features associated with mode coupling transition lines of the types B and A at, respectively, small and very large size disparities. Both lines might merge, at some intermediate disparity, at a higher-order point, to which logarithmic relaxation would be associated. This picture resembles predictions of a recent mode coupling theory for fluids confined in matrices with interconnected voids [V. Krakoviack, Phys. Rev. Lett. 94, 065703 (2005)].     

Effects of molecular association on polarizability relaxation in liquid mixtures of benzene and hexafluorobenzene

In this work we have studied the relaxation dynamics of the many-body polarizability anisotropy in liquid mixtures of benzene (Bz) and hexafluorobenzene (Hf) at room temperature by femtosecond optical heterodyne-detected Raman-induced Kerr effect spectroscopy (OHD-RIKES) experiments and molecular dynamics (MD) simulations. The computed polarizability response arising from intermolecular interactions was included using the first-order dipole-induced-dipole model with the molecular polarizability distributed over the carbon sites of each molecule. We found good qualitative agreement between experiments and simulations in the features exhibited by the nuclear response function R(t) for pure liquids and mixtures. The long-time diffusive decay of R(t) was observed to vary substantially with composition, slowing down noticeably with dilution of each of the species as compared with that in the corresponding pure liquids. MD simulation shows that the effect on R(t) is due to the formation of strong and localized intermolecular association between Bz and Hf species that hinder the rotational diffusive dynamics. The formation of these Bz-Hf complexes in the liquid mixtures also modifies the rotational diffusive dynamics of the component species in such a way that cannot be explained solely in terms of a viscosity effect. Even though the computed orientational diffusive relaxation times associated with Bz and Hf are larger by a factor of approximately 2 than those from experiments, we found similar trends in experiments and simulations for these characteristic times as a function of composition. Namely, the collective and single-molecule orientational correlation times associated with Bz are observed to grow monotonically with the dilution of Bz, while those corresponding to Hf species exhibit a maximum at the equimolar composition. We attribute the quantitative discrepancy between experiments and simulations to the use of the Williams potential, which seems to overestimate the intermolecular interactions and thus predicts not only a slower translational dynamics but also a slower rotational diffusion dynamics than in real fluids.     

Relaxation dynamics in tert-butylpyridine/tristyrene mixture investigated by broadband dielectric spectroscopy

We investigated, by means of dielectric spectroscopy, the relaxation dynamics of glass forming binary mixtures composed by the quite rigid polar molecules tert-butylpyridine dissolved in the apolar solvent tristyrene. By changing the relative concentration of the components we observed a transition from a relaxation scenario with a structural process and an excess wing to that with a structural process and a well resolved secondary process. Another relaxation process, slower than the latter, was observed, well below Tg. Our detailed analysis evidenced that the secondary relaxation with shorter relaxation time can be identified as the Johari-Goldstein relaxation for all the mixtures, whereas the new relaxation process was attributed to a different type of motion of tert-butylpyridine needing a larger amount of free volume for the molecular rotation.     

Dynamic arrest in a liquid of symmetric dumbbells: reorientational hopping for small molecular elongations

We present extensive equilibrium and out-of-equilibrium molecular-dynamics simulations of a liquid of symmetric dumbbell molecules, for constant packing fraction, as a function of temperature and molecular elongation. We compute diffusion constants as well as odd and even orientational correlators. The notations odd and even refer to the parity of the order l of the corresponding Legendre l polynomial, evaluated for the orientation of the molecular axis relative to its initial position. Rotational degrees of freedom of order l are arrested if, in the long-time limit, the corresponding orientational l correlator does not decay to zero. It is found that for large elongations translational and rotational degrees of freedom freeze at the same temperature. For small elongations only the even rotational degrees of freedom remain coupled to translational motions and arrest at a finite common temperature. On the contrary, the odd rotational degrees of freedom remain ergodic at all investigated temperatures. Hence, in the translationally arrested state, each molecule remains trapped in the cage formed by its neighboring molecules, but is able to perform 180 degrees rotations, which lead to relaxation only for the odd orientational correlators. The temperature dependence of the characteristic time of these residual rotations is well described by an Arrhenius law. Finally, we discuss the evidence in favor of the presence of the type-A transition for the odd rotational degrees of freedom, as predicted by mode-coupling theory for small molecular elongations. This transition is distinct from the type-B transition, associated with the arrest of the translational and even rotational degrees of freedom for small elongations, and with all degrees of freedom for large elongations. Odd orientational correlators are computed for small elongations at very low temperatures in the translationally arrested state. The obtained results suggest that hopping events restore the ergodicity of the odd rotational degrees of freedom at temperatures far below the A transition.     

Ideal mixing behavior of the debye process in supercooled monohydroxy alcohols

Glass-forming monohydroxy alcohols exhibit two dielectric relaxation signals with super-Arrhenius temperature dependence: a Debye peak and an asymmetrically broadened alpha-process. We explore the behavior of these distinct relaxation features in mixtures of such liquids by dielectric measurements. The study focuses on the viscous regime of two binary systems: 2-methyl-1-butanol with 2-ethyl-1-hexanol and 1-propanol with 3,7-dimethyl-1-octanol. We find that the logarithmic relaxation time, log(tau), of the Debye peak follows an ideal mixing law (linear change with mole fraction), even in the case of mixing structurally dissimilar components. By contrast, the log(tau) versus mole fraction curve for the alpha-process is nonlinear, indicative of slower structural relaxation relative to the expectation on the basis of ideal mixing behavior. The latter observation is analogous to the effect of composition on viscosity, heat of mixing, and glass-transition temperature, whereas the ideal mixing of log(tau) seen for the Debye peak is the exception. We conclude that the unusual ideal mixing behavior of dielectric relaxation in monohydroxy alcohols is not a result of structural similarity, but rather yet more evidence of the Debye process being decoupled from other dynamic and thermodynamic properties.     

The protein "glass" transition and the role of the solvent

Hydrated proteins undergo a change in their dynamical properties in the neighborhood of a temperature. The change of dynamics has been likened to glass transition of glass-forming substances because similar properties were found. However, a complete understanding of the conformation fluctuations of hydrated proteins and their relation to the dynamics of the solvent is still not available, possibly due to the protein molecules being more complex than ordinary glass-formers. For this reason, we turn our attention to the experimental findings of the dynamics of mixtures of water with simpler glass-formers (small molecules and polymers). Two major relaxation processes have been observed in these aqueous mixtures. One is the structural alpha-relaxation of the hydrophilic glass-former hydrogen bonded to the water, which is responsible for glass transition. The other one is the local secondary beta-relaxation of water in the mixture. Remarkably, these two relaxation processes in aqueous mixtures have analogues in hydrated proteins with the same properties. The conformation fluctuations of the protein and the relaxation of the solvent in hydrated proteins behave like the alpha-relaxation of the hydrophilic glass-former hydrogen bonded to the water and the beta-relaxation of water in other aqueous mixtures, respectively. At low temperatures, the Arrhenius activation energy of the relaxation time of the solvent in a hydrated protein is almost the same as that of the beta-relaxation of water in the glassy states of aqueous mixtures. The Arrhenius T-dependence of the solvent relaxation times no longer holds at temperatures that exceed the "glass" transition temperature of the hydrated protein, defined as the temperature at which the conformation relaxation time is very long. This behavior of the solvent in hydrated proteins is similar to that found in the beta-relaxation of water in aqueous mixtures when crossing the glass transition temperature of the mixture (Capaccioli, S.; Ngai, K. L.; Shinyashiki, N. J. Phys. Chem. B 2007, 111, 8197). Furthermore, the same dynamics were found in mixtures of two van der Waals glass-formers, which are even simpler systems than aqueous mixtures because of the absence of hydrogen bonding. The experimental data of these ideal mixtures of van der Waals glass-formers have been given a satisfactory theoretical explanation. Since the properties of hydrated proteins, aqueous mixtures, and the mixtures of van der Waals liquids are similar, we transfer the theoretical understanding gained in the study of the last system sequentially to the two other increasingly more complex systems.     

Identification of dielectric and structural relaxations in glass-forming secondary amides

Dielectric relaxation dynamics of secondary amides is explored in their supercooled state near the glass transition temperature Tg by investigating N-ethylacetamide and its mixtures with N-methylformamide. All the samples are found to exhibit giant dielectric permittivities, reaching over 500 in N-methylformamide-rich mixtures around Tg. For both the neat and binary systems, the predominant relaxation peak is of the Debye-type throughout the viscous regime, which is an unexpected feature for a glass former with intermediate fragility. The present results combined with the earlier reported high-temperature data reveal that the dielectric strength delta epsilon(D) of the Debye relaxation extrapolates to zero at frequencies of 10(10)-10(11) Hz, which is about two orders of magnitude lower than the phonon frequency limit typical of the structural relaxation. This Debye process is remarkably similar to the dielectric behavior of many monohydroxy alcohols, which implies a common nature of purely exponential relaxation dynamics in these liquids. Based on the dielectric properties, we conclude that the Debye relaxation in the secondary amides is not a direct signature of the primary or alpha-relaxation, the latter being obscured at low temperatures due to the relatively low permittivity and close spectral proximity to the Debye peak. As in the case of monohydroxy alcohols, dielectric polarization and structure fluctuate on different time scales in secondary amides. The Kirkwood-Fr?hlich correlation factors for Debye-type liquids are also discussed.     

Dynamics of polypropylene chains in their binary blends of different stereochemical sequences studied by Monte Carlo simulations

The conformational and dynamic properties of polypropylene （PP） for both pure melts and blends with different chain tacticity were investigated by Monte Carlo simulation of isotactic （iPP）, atactic （aPP） and syndiotactic （sPP） polypropylenes. The simulation of coarse-grained PP models was performed on a high coordination lattice incorporating short- and long-range intramolecular interactions from the rotational isomeric state （RIS） model and Lennard-Jones （LJ） potential function of propane pairs, respectively. The dynamics of chains in binary PP/PP mixture were investigated with the composition of C150H302 with different chain taciticity. The diffusion rates of PP with different stereochemistry are generally in the order as： iPP 〉 aPP 〉〉 sPP. For PP/PP blends with 50：50 wt% binary mixtures, immiscibility was observed when sPP was introduced into the mixtures. The diffusion rate of iPP and aPP became slower after mixing, while sPP diffuses significantly faster in the binary mixtures. The mobility of PP chains depends on both intramolecular （molecular size and chain stiffness） and intermolecular （chain packing） interactions. The effect of intramolecular contribution is greater than that of intermolecular contribution for iPP and aPP chains in binary mixtures. For sPP chain, intermolecular interaction has greater influence on the dynamics than intramolecular contribution.     

Glasslike behavior in aqueous electrolyte solutions

When salts are added to water, generally the viscosity increases, suggesting that the ions increase the strength of the water's hydrogen-bond network. However, infrared pump-probe measurements on electrolyte solutions have found that ions have no influence on the rotational dynamics of water molecules, implying no enhancement or breakdown of the hydrogen-bond network. Here, we report optical Kerr effect and dielectric relaxation spectroscopic measurements, which have enabled us to separate the effects of rotational and transitional motions of the water molecules. These data show that electrolyte solutions behave like a supercooled liquid approaching a glass transition in which rotational and translational molecular motions are decoupled. It is now possible to understand previously conflicting viscosity data, nuclear magnetic resonance relaxation, and ultrafast infrared spectroscopy in a single unified picture.     

Superdipole liquid scenario for the dielectric primary relaxation in supercooled polar liquids

We propose a dynamic structure of coupled dynamic molecular strings for supercooled small polar molecule liquids and accordingly we obtain the Hamiltonian of the rotational degrees of freedom of the system. From the Hamiltonian, the strongly correlated supercooled polar liquid state is renormalized to a normal superdipole liquid state. This scenario describes the following main features of the primary or alpha-relaxation dynamics in supercooled polar liquids: (1) the average relaxation time evolves from a high temperature Arrhenius to a low temperature non-Arrhenius or super-Arrhenius behavior; (2) the relaxation function crosses over from the high temperature exponential to low temperature nonexponential form; and (3) the temperature dependence of the relaxation strength shows non-Curie features. According to the present model, the crossover phenomena of the first two characteristics arise from the transition between the superdipole gas and the superdipole liquid. The model predictions are quantitatively compared with the experimental results of glycerol, a typical glass former.     

Steering and ro-vibrational effects on dissociative adsorption and associative desorption of H2/Pd(100)

The interaction of hydrogen with many transition metal surfaces is characterized by a coexistence of activated with non-activated paths to adsorption with a broad distribution of barrier heights. By performing six-dimensional quantum dynamical calculations using a potential energy surface derived from ab initio calculations for the system H₂/Pd(100) we show that these features of the potential energy surface lead to strong steering effects in the dissociative adsorption and associative desorption dynamics.

In particular, we focus on the coupling of the translational, rotational and vibrational degrees of freedom of the hydrogen molecule in the reaction dynamics.     

Experimental evidence for excess entropy discontinuities in glass-forming solutions

Glass transition temperatures T(g) are investigated in aqueous binary and multi-component solutions consisting of citric acid, calcium nitrate (Ca(NO(3))(2)), malonic acid, raffinose, and ammonium bisulfate (NH(4)HSO(4)) using a differential scanning calorimeter. Based on measured glass transition temperatures of binary aqueous mixtures and fitted binary coefficients, the T(g) of multi-component systems can be predicted using mixing rules. However, the experimentally observed T(g) in multi-component solutions show considerable deviations from two theoretical approaches considered. The deviations from these predictions are explained in terms of the molar excess mixing entropy difference between the supercooled liquid and glassy state at T(g). The multi-component mixtures involve contributions to these excess mixing entropies that the mixing rules do not take into account.     

Exponential probe rotation in glass-forming liquids

Using time resolved optical depolarization, we have studied the rotational behavior of molecular probes in supercooled liquids near the glass transition temperature T(g). Simultaneously, the dynamics of the liquid immediately surrounding these rigid probes is measured by triplet state solvation experiments. This direct comparison of solute and solvent dynamics is particularly suited for assessing the origin of exponential orientational correlation functions of probe molecules embedded in liquids which exhibit highly nonexponential structural relaxation. Polarization angle dependent Stokes shift correlation functions demonstrate that probe rotation time and solvent response time are locally correlated quantities in the case of smaller probe molecules. Varying the size of both guest and host molecules shows that the size ratio determines the rotational behavior of the probes. The results are indicative of time averaging being at the origin of exponential rotation of probes whose rotational time constant is slower than solvent relaxation by a factor of 20 or more.     

Some structural aspects in binary aqueous mixtures of simple amides from rotational molecular motions

Nuclear magnetic relaxation rates of²D and¹⁴N in binary aqueous mixtures of formamide,N-methylformamide (NMF), andN,N-dimethylformamide (DMF) are reported as a function of the mixture composition. From these intramolecular quadrupolar relaxation data separate rotational correlation times for the two components of the mixture can be determined. The relative variation of the single correlation time as a function of the composition is interpreted in terms of structural changes caused by hydrogen bonding and hydrophobic effects. The results also clearly reflect the expected characteristic variation of these effects on the rotational molecular motions in going from formamide to NMF and DMF. The maximum correlation time retardation of DMF in the aqueous mixture is compared with those of other hydrophobic solvents. A correlation between this maximum retardation and the excess enthalpy of mixing of hydrophobic solvents in aqueous solution can be established graphically.     

New thermal diffusion coefficient measurements for hydrocarbon binary mixtures: viscosity and composition dependency

New thermal diffusion coefficients of binary mixtures are measured for n-decane-n-alkanes and 1-methylnaphthalene-n-alkanes with 25 and 75 wt % at 25 degrees C and 1 atm using the thermogravitational column technique. The alkanes range from n-pentane to n-eicosane. The new results confirm the recently observed nonmonotonic behavior of thermal diffusion coefficients with molecular weight for binary mixtures of n-decane- n-alkanes at the compositions studied. In this work, the mobility and disparity effects on thermal diffusion coefficients are quantified for binary mixtures. We also show for the binary mixtures studied that the thermal diffusion coefficients and mixture viscosity, both nonequilibrium properties, are closely related.     

Dynamic light scattering in mixed alkali metaphosphate glass forming liquids

We report the first ever photon correlation spectroscopy performed on single alkali and mixed alkali metaphosphate glasses at refractory temperatures above the glass transition. We find not only a significant decrease in the glass transition temperature but also a decrease in fragility for the mixed alkali composition as compared with the single akali glasses. We argue that structural relaxation in these polymeric oxide glasses is largely controlled by the cross linking cations and that the changes in fragility that we observed are a reflection of changes in the cooperativity of structural relaxation wrought by the substantial decrease in the ion mobility that accompanies the mixing of alkali ions.     

Individual degrees of freedom and the solvation properties of water

Using molecular dynamics simulations in conjunction with home-developed Split Integration Symplectic Method we effectively decouple individual degrees of freedom of water molecules and connect them to corresponding thermostats. In this way, we facilitate elucidation of structural, dynamical, spectral, and hydration properties of bulk water at any given combination of rotational, translational, and vibrational temperatures. Elevated rotational temperature of the water medium is found to severely hinder hydration of polar molecules, to affect hydration of ionic species in a nonmonotonous way and to somewhat improve hydration of nonpolar species. As proteins consist of charged, polar, and nonpolar amino-acid residues, the developed methodology is also applied to critically evaluate the hypothesis that the overall decrease in protein hydration and the change in the subtle balance between hydration of various types of amino-acid residues provide a plausible physical mechanism through which microwaves enhance aberrant protein folding and aggregation.