Structural relaxation in complex liquids: non-Markovian dynamics in a bistable potential

The time correlation function C(t) identical with of the distance fluctuations of a particle moving in a bistable potential under the action of fractional Gaussian noise (fGn) is calculated from a Smoluchowski-type equation derived from a generalized Langevin equation (GLE). The time derivative of this function, dC(t)dt, is compared with data from optical Kerr effect measurements of liquid crystal dynamics in the vicinity of the isotropic-to-nematic transition, which are related to the time derivative of an orientational correlation function. A number of characteristic features of the experimental decay curves, including short and intermediate time power law behavior and long time exponential relaxation, are qualitatively reproduced by the analytical calculations, even though the latter do not explicitly treat orientational degrees of freedom. The GLE formalism with fGn was, in fact, originally proposed as a model of protein conformational fluctuations, so the present results suggest that it may also serve more generally as a model of structural relaxation in complex condensed phase media.     

Shear stress relaxation in liquids

We show that at high densities, as the system size decreases, liquid becomes able to permanently sustain increasing internal shear stress after a constant deformation, although the other characteristic liquid properties, such as the pair distribution function and diffusion coefficient do not change under strain. The system size necessary for observation of this effect increases with the decrease in temperature, and it is stronger in pair potentials with steeper repulsive part. We relate this result to the size of the "cooperatively rearranging regions" of the Adam-Gibbs theory of glass transition.     

Intermolecular vibrational relaxation in liquids

The influence of intermolecular vibrational relaxation on dipole moment correlation functions, as obtained from IR band shapes, is discussed. It is explicitly shown that vibrational relaxation due to intermolecular interactions depends on the reorientational behaviour of the molecules in the liquid.Therefore, an a priori separation of the dipole moment correlation function into independent reorientational and vibrational factors is not generally possible. The implications for various procedures used to “correct” Raman and IR band shapes for vibrational relaxation are discussed.The expression derived for the intermolecular vibrational relaxation is used to calculate theoretically the effect of transition dipole-transition dipole coupling on dipole moment correlation functions.Experimental data obtained from isotopic dilution measurements support the interpretation of the isotopic dilution effect in terms of the transition dipole-transition dipole coupling.     

Non-equilibrium shear relaxation in liquids

A theory for non-equilibrium shear relaxation in liquids at low frequencies is presented. It is based on molecular considerations used in theories of low frequency depolarized light scattering.The results for the complex shear impedance contain terms in addition to those obtained by the phenomenological relaxation theory.     

Spin-rotation relaxation in liquids for dynamically coherent reorientation

It is estimated that for liquids in which the molecular reorientation is dynamically coherent the nuclear spin relaxation rate due to spin-rotation interaction increases with temperature approximately as T^{$\text{1}\text{2}$}.     

Dynamics of glass-forming liquids. IX. Structural versus dielectric relaxation in monohydroxy alcohols

The prominent Debye-type but non-Arrhenius dielectric relaxation is a feature common to many monohydroxy alcohols in their liquid state. Although this exponential process is often considered to reflect the primary structural relaxation, only a faster, smaller, and nonexponential relaxation peak correlates with viscous flow and mechanical relaxation. We provide dielectric relaxation data for 2-methyl-1-butanol, 2-ethyl-1-hexanol, and 3,7-dimethyl-1-octanol across ten decades in time. Based on these and previous results, we show that there exists a variety of dielectric to mechanical relaxation time ratios in the viscous regime, but a universal value of 100 for that ratio appears to evolve in the high temperature limit. The temperature dependence for both the relaxation time and strength of the Debye peak differs from the typical behavior of structural dynamics in terms of the alpha process. The implications of these findings for rationalizing the Debye-type dielectric process of hydrogen-bonded liquids are discussed.     

Structural relaxation in the hydrogen-bonding liquids N-methylacetamide and water studied by optical Kerr effect spectroscopy

Structural relaxation in the peptide model N-methylacetamide (NMA) is studied experimentally by ultrafast optical Kerr effect spectroscopy over the normal-liquid temperature range and compared to the relaxation measured in water at room temperature. It is seen that in both hydrogen-bonding liquids, beta relaxation is present, and in each case, it is found that this can be described by the Cole-Cole function. For NMA in this temperature range, the alpha and beta relaxations are each found to have an Arrhenius temperature dependence with indistinguishable activation energies. It is known that the variations on the Debye function, including the Cole-Cole function, are unphysical, and we introduce two general modifications: One allows for the initial rise of the function, determined by the librational frequencies, and the second allows the function to be terminated in the alpha relaxation.     

Moderately and strongly supercooled liquids: a temperature-derivative study of the primary relaxation time scale

The primary relaxation time scale tau(T) derived from the glass forming supercooled liquids (SCLs) is discussed within ergodic-cluster Gaussian statistics, theoretically justified near and above the glass-transformation temperature T(g). An analysis is given for the temperature-derivative data by Stickel et al. on the steepness and the curvature of tau(T). Near the mode-coupling-theory (MCT) crossover T(c), these derivatives separate by a kink and a jump, respectively, the moderately and strongly SCL states. After accounting for the kink and the jump, the steepness remains a piecewise conitnuous function, a material-independent equation for the three fundamental characteristic temperatures, T(g), T(c), and the Vogel-Fulcher-Tamman (VFT) T(0), is found. Both states are described within the heterostructured model of solidlike clusters parametrized in a self-consistent manner by a minimum set of observable parameters: the fragility index, the MCT slowing-down exponent, and the chemical excess potential of Adam and Gibbs model (AGM). Below the Arrhenius temperature, the dynamically and thermodynamically stabilized clusters emerge with a size of around of seven to nine and two to three molecules above and close to T(g) and T(c), respectively. On cooling, the main transformation of the moderately into the strongly supercooled state is due to rebuilding of the cluster structure, and is attributed to its rigidity, introduced through the cluster compressibility. It is shown that the validity of the dynamic AGM (dynamically equivalent to the standard VFT form) is limited by the strongly supercooled state (T(g) < T < T(c)) where the superrigid cooperative rearranging regions are shown to be well-chosen parametrized solidlike clusters. Extension of the basic parameter set by the observable kinetic and diffusive exponents results in prediction of a subdiffusion relaxation regime in SCLs that is distinct from that established for amorphous polymers.     

Temperature-dependent 11B spin-lattice relaxation time for BF4 and CF3BF3 anions in room-temperature ionic liquids

Temperature-dependent (11)B T(1) values were measured for the BF(4) anion and BF(3) in the CF(3)BF(3) anion in room-temperature ionic liquids (RTILs) composed of the cation N-diethyl-N-methyl-N-(2-methoxyethyl)ammonium (DEME). Including the lithium-salt-doped samples, two neat and two binary ionic liquids were studied. Arrhenius plots of the (11)B T(1) showed T(1) minima for BF(4) in the temperature range between 243 (or above freezing) and 373 K. Using the Bloembergen, Pound, and Purcell(BPP) equations for the (11)B quadrupolar and (11)B-(19) F dipolar relaxation mechanisms, the correlation times for motions of BF(4) were calculated. Since the internal rotation of BF(3) is assumed in CF(3)BF(3), T(1) minimum was not observed. The effects of the addition of the lithium salt on the (11)B correlation time and (11)BT(1) for the anions in the ILs are discussed.     

Molecular kerr relaxation theory for nondipolar liquids in reorienting pulse fields

The time variations of the difference in refractive index in optical birefringence are calculated for a liquid composed of nondipolar anisotropically polarizable molecules acted on by reorienting pulse fields. The molecular dynamics is based on Sack's equation, taking into account small inertial effects (a modification of the Smoluchowski rotational diffusion equation). The time variations in birefringence are analyzed for rectangular and cosine pulse shapes on the basis of Sack's equation and are plotted for a gaussian pulse on the basis of Smoluchowski's equation. Measurements are proposed of the birefringence component with frequency 4ω related to the square of the electric anisotropy reorientation parameter of the molecules.     

Heterogeneous thermal excitation and relaxation in supercooled liquids

We investigate a phenomenological model which rationalizes the effects of dielectric hole burning on the basis of heterogeneous dielectric and specific heat relaxation in supercooled liquids. The quantitative agreement between model predictions and dielectric hole-burning observations is lost if the assumption of correlated dielectric and thermal relaxation times is removed from the model. This suggests that dynamically distinct domains in real liquids are associated with a time constant which characterizes both the structural and thermal relaxation behaviors. The calculations demonstrate that the observed burn-induced modifications reflect the spectral selectivity and persistence time of the fictive temperatures within these domains, and that 100 or more cycles of the sinusoidal burn field can be required to saturate the heat accumulated in the slow degrees of freedom. It is also shown that the recovery of dielectric holes is entirely accounted for by the model, and that the persistence times do not provide direct insight into rate exchange processes. Additionally, the model predicts that the heating effects considered here are a significant source of nonlinear dielectric behavior, even in the absence of deliberate frequency selective hole burning.     

Electric-field-induced changes in spin-lattice relaxation in polar liquids

Spin—lattice relaxation times of acetonitrile, aligned by an electric field, have been measured. In contrast to earlier investigations on other polar liquids, no electric-field effects on T₁ could be established. The apparent discrepancy is discussed in terms of electric conduction and inhomogeneity of the applied electric field.     

Vibrational energy relaxation of large-amplitude vibrations in liquids

Given the limited intermolecular spaces available in dense liquids, the large amplitudes of highly excited, low frequency vibrational modes pose an interesting dilemma for large molecules in solution. We carry out molecular dynamics calculations of the lowest frequency ("warping") mode of perylene dissolved in liquid argon, and demonstrate that vibrational excitation of this mode should cause identifiable changes in local solvation shell structure. But while the same kinds of solvent structural rearrangements can cause the non-equilibrium relaxation dynamics of highly excited diatomic rotors in liquids to differ substantially from equilibrium dynamics, our simulations also indicate that the non-equilibrium vibrational energy relaxation of large-amplitude vibrational overtones in liquids should show no such deviations from linear response. This observation seems to be a generic feature of large-moment-arm vibrational degrees of freedom and is therefore probably not specific to our choice of model system: The lowest frequency (largest amplitude) cases probably dissipate energy too quickly and the higher frequency (more slowly relaxing) cases most likely have solvent displacements too small to generate significant nonlinearities in simple nonpolar solvents. Vibrational kinetic energy relaxation, in particular, seems to be especially and surprisingly linear.     

Application of various ionic liquids as cosolvents for chloroperoxidase-catalysed biotransformations

Abstract  Chloroperoxidase from Caldariomyces fumago catalyses oxidation of indole and thioanisole in reaction mixtures containing up to 40% (v/v) of different ionic liquids (ILs). Results indicate that ILs containing tosylate, trifluoroacetate, chloride, and methylsulfate anions are suitable cosolvents for these transformations, yielding high enantiomeric excess and good conversion rates. Graphical abstract       

Application of various ionic liquids as cosolvents for chloroperoxidase-catalysed biotransformations

Abstract  

Chloroperoxidase from Caldariomyces fumago catalyses oxidation of indole and thioanisole in reaction mixtures containing up to 40% (v/v) of different ionic liquids (ILs). Results indicate that ILs containing tosylate, trifluoroacetate, chloride, and methylsulfate anions are suitable cosolvents for these transformations, yielding high enantiomeric excess and good conversion rates.     

Direct computation of characteristic temperatures and relaxation times for glass-forming polymer liquids

Characteristic temperatures and structural relaxation times for different classes of glass-forming polymer liquids are computed using a revised entropy theory of glass formation that permits the chain backbone and the side groups to have different rigidities. The theory is applied to glass formation at constant pressure or constant temperature. Our calculations provide new insights into physical factors influencing the breadth of the glass transition and the associated growth of relaxation times.