Volume 223, Issue 9 -

We report recent efforts to understand the new MIT-Messina experimental discovery of a dynamic crossover at low temperatures in confined water. Preliminary calculations are not inconsistent with one tentative interpretation of this dynamic crossover as resulting from the system passing from the high-temperature high-pressure "HDL" side of the Widom line (where the liquid might display fragile behavior) to the low-temperature low-pressure "LDL" side of the Widom line (where the liquid might display strong behavior). The Widom line - defined to be the line in the pressure-temperature plane where the correlation length has its maximum - arises only if there is a critical point. Hence interpreting the MIT experiments in terms of a Widom line is of potential relevance to testing experimentally, for confined water, the liquid-liquid critical point hypothesis.

In the present article we show how models for simple liquids can be used to describe the dynamics of atoms in molecular liquids within the rigid molecule approximation. We show in particular that the atomic masses are to be replaced by the corresponding Sachs-Teller masses and we derive a formal expression for the so-called Einstein frequency. The approach is illustrated for a model which has been originally developed for simple liquids and which has been used in the past to analyze quasielastic neutron scattering data from pure water and dilute aqueous solutions of apolar molecules. We obtain a remarkable agreement with results from molecular dynamics simulations not only in the quasielastic, diffusive regime, but also in the inelastic regime corresponding to intermolecular vibrations and fast molecular librations.

The structural transformation of different high-density amorphous (HDA) ice modifications into the low-density amorphous (LDA) ice is studied by small-angle neutron scattering (SANS) techniques. All experiments have been performed at stationary conditions allowing to collect detailed information not only on the SANS formfactor but also on its time evolution and, hence, the kinetics governing the transformation process. A parametrization of the SANS formfactor by a superposition of the Debye-Bueche formfactor, characterizing a non-particulate two phase mixture, and a Porod-limit scattering formfactor is carried out successfully. The Porod-limit scattering indicates the presence of sharp interfaces and surfaces present in the sample material. Interpreting this signal as due to a grainy consistency of the amorphous samples grain sizes of the order of at least some micrometers can be approximated. The Debye-Bueche ansatz accounts for the formation of a transient pronounced signal on mesoscopic length scales. Its analysis results in an average domain size of 12–16 Å characterizing a hypothetical two phase mixture in its state of strongest intermixture, i.e., strongest heterogeneity. Interpretation of the Debye-Bueche formfactor by the Porod invariant results in a sample contrast that is by a factor of about 4 smaller than a hypothetical first-order transition between any modification of HDA and LDA. This statement is valid for an unstrained two-phase system separated by sharp interfaces. A detailed discussion is given which tries to set the present results into a more realistic context.

The unusual increase of diffusivity of supercooled water upon compression seems to be related to the existence of at least two major distinct local structural forms: a "low-density" structure, exhibiting an almost perfect tetrahedral hydrogen bonding network, and a "high-density" structure, characterized by defects in this network. The structural changes can be measured by the "tetrahedricity parameter", describing the deviation from the ideal tetrahedron. In this paper we show that the anomalous diffusion behavior upon compression cannot only be related to the structural heterogeneities but also to dynamical heterogeneities occuring in supercooled liquid water. This is shown for translational heterogeneities which decrease with temperature and pressure. Both, static and dynamic heterogeneities can be correlated. They are substantial at low temperatures and moderate pressures and diminish with increasing temperature and pressure, respectively. Our results are based on molecular dynamics simulations of the TIP4P-Ew water model [1].

Using a set of IR spectroscopy methods the OH- and OD-stretch region of H 2 O, D 2 O and HDO were investigated. With a combination of attenuated total reflection infrared (ATR-IR) and transmission infrared Fourier Transform spectroscopy, temperature dependent experiments were carried out. HDO experiments were done with varying isotopic concentrations. We focused on contributions at higher wavenumbers within the OH/OD-stretch region to discuss coupling effects. We also compared results from ATR and transmission spectroscopy in order to check the comparability of these techniques. In addition we tried to investigate how the overtone of the bending vibration may be included into the analysis of the OH-stretch region of pure water.

Percolation transitions of water and solute molecules in an ideal completely miscible aqueous solution are studied by computer simulations. Three concentration ranges with different kinds of water and solute clustering can be distinguished. An infinite water network, present in pure liquid water, breaks at some solute concentration. Accordingly, the infinite network of solute molecules, present in pure liquid solute, breaks upon addition of water. At ambient and high temperatures, there is a concentration range were both components are below their respective percolation thresholds and there are no water or solute infinite networks. The existence of such concentration range is a characteristic of a completely miscible binary mixture. Upon supercooling, the threshold concentrations decrease and simultaneous existence of the infinite networks of water and of solute becomes possible. The presence of two inter-penetrating infinite networks of molecules may be one of the conditions required for the liquid-liquid transition of one-component isotropic fluid.

In this study, we investigate the self-diffusion coefficient, the shear viscosity and the thermal conductivity of a single-component system interacting via a Gaussian core (GC) potential. The transport properties are studied by means of the Green-Kubo formulas calculated from molecular dynamics simulation. We show that, for certain state conditions, anomalous behaviour occurs for the diffusivity and the shear viscosity. Therefore, the Stokes-Einstein relation is violated for the GC fluid. We do not find anomalous behaviour for the thermal conductivity. We develop an equation of state for the deviation of the ideal gas pressure and we derive the excess entropy from this equation. Depending on the phase space region, the excess entropy also shows anomalous behaviour. We discuss recently developed scaling relationships between excess entropy and transport properties. Because the GC potential is bounded, these relationships do not work properly for the GC fluid. Using new empirical scaling relations we are able to fit the diffusion coefficient within one single master curve for the whole density and temperature range we have simulated. We were also able to find a single master curve for the viscosity, but only for state conditions where the classical Stokes-Einstein relation is valid.

It is an open question whether high density amorphous (HDA) ice is a glassy material structurally related to an ultraviscous high density liquid (HDL) or a nanocrystalline material unrelated to a liquid. In order to shed light on this question we have performed molecular dynamics simulations on a HDA model system at a pressure of p ≈ 0.3 GPa using the COMPASS force field. After removing the irreversible structural relaxation effect by initial isobaric heating/cooling cycles, we observe a deviation from linearity in the density vs. temperature plot in the range 170 ± 15 K in subsequent cycles, which we attribute to the glass-transition temperature T g . This assignment of T g is corroborated by two independent methods, namely from a rapid increase in the diffusion coefficient at ≈169 K and a deviation from linearity at ≈174 K in an enthalpy versus temperature plot. The structure of the model system is in good agreement with the experimentally determined structure of HDA. We, thus, suggest that HDA may indeed be a low temperature structural proxy of an ultraviscous liquid HDL.

The influence of incorporating the polypeptide gramicidin on the lateral mobility of the monoacylglyceride monoolein (MO) in its bicontinuous cubic lipid mesophases is studied applying static field gradient NMR. The effects of gramicidin on the topology, structure and phase behaviour of the system are characterized by small-angle x-ray scattering (SAXS) experiments. On the structural level the experiments show significant shifts in the boundaries of the various mesophases. Measurements of the translational dynamics are restricted to cubic mesophases, where the diffusion coefficients of lipid and additive are determined both by geometrical obstruction and by lipid-protein interaction effects.

In a series of experiments we measured the mechanical properties of single alginate beads by means of squeezing experiments between two parallel plates. We used multivalent counter-ions as cross-linking molecules for the formation of three dimensional alginate gels. In this article we examined pure Fe(II) (ferric), Fe(III) (ferrous) and Ca(II) (calcium) ions as cross-linking agents and different mixtures between these charged compounds. The results of squeezing experiments showed that capsules formed with pure ferrous ions were less stable than particles which were cross-linked with calcium or ferric ions. It turned out that at equal molar concentrations calcium and ferrous ions formed stronger gels than ferric ions. In addition to squeezing capsule experiments we also investigated different particles by optical microscopy and scanning electron microscopy. Experiments of Energy-dispersive X-ray spectroscopy (EDAX) show different compositions of these beads.

We simulate the solubility and solvation free energy of methane dissolved in water at infinite dilution. Molecular dynamics simulations of TIP4P-Ew model water are carried out at ambient pressure conditions over a large temperature interval, ranging from 250 K to 370 K. Solvation free energies are determined using the Widom particle insertion method. The fitted temperature dependent data is used to calculate solvation enthalpies, entropies, as well as the heat capacity of solvation. In particular we study the effect of polarizability of methane on those thermodynamic parameters. Solute polarization leads to a lowering of the solvation free energy at 298 K to 8.3 kJ mol −1 , almost exactly matching the experimental value. A close inspection of the enthalpic and entropic contributions, however, reveals that this coincidence is a consequence of a compensation of enthalpic and entropic contributions, each of them deviating even larger from their respective experimental values. Surprisingly, the solute polarizability is apparently affecting the solvation entropy more strongly than the solvation enthalpy, leading to an about 5 J K −1 mol −1 smaller (less negative) solvation entropy compared to the non-polarizable model. The solute-water radial distribution functions of the polarizable particle reveals significant modifications, favoring small distances, as well as structural changes, very similar to those caused by a temperature increase. This is suggesting that the reduced negative solvation entropy of a polarizable methane particle is related to a more disordered, "high-temperature"-like hydration shell.

The acid-induced unfolding of myoglobin and its haem-free derivative apo-myoglobin is studied by broadband dielectric relaxation spectroscopy at pH values near 5, 4 and 2, which reflect the transition N → MG → U A from the native state (N) via a molten globule state (MG) to an acid-unfolded state (U A ). Spectral changes are singled out by considering difference spectra for the transitions N → MG and N → U A . A pronounced increase of the amplitude of the tumbling motion of holo-myoglobin and apo-myoglobin in the sequence N → MG→ U A reflects the increase of their electrical dipole moments by progressive unfolding. A distinct high-frequency shoulder of the tumbling mode indicates an enhanced internal protein dynamics in the unfolded states. The calculated Stokes radii confirm a compact nature of the MG state and a large increase in size of the U A state relative to the native state. In the native state the Stokes radii deduced from the dielectric spectra agree fairly well with those deduced from dynamic light scattering. In the MG state, and particularly in the U A state, the Stokes radii determined by light scattering are markedly larger than those determined by dielectric relaxation. The difference is attributed to aggregation of the unfolded species, which affects dynamic light scattering more than dielectric relaxation. In the high-frequency regime, the dielectric spectra indicate that unfolding enhances the number of water molecules showing bulk-like dynamics, but the effect is rather weak.

Various distribution functions of hydrogen bond lifetimes, used to describe the dynamics of breakage and formation of these bonds are calculated for a molecular dynamics model of water of 3456 molecules at 310 K. Quenched (inherent) structures are derived from instantaneous MD structures. Comparing the distribution functions from I and Q structures allows interpreting their characteristic features. The sharp peak at ~15 fs, which prevails in the most frequently used distributions, is ascribed to short-lived “false” H bonds which results from violations of hydrogen bonding criteria induced by dynamic intermolecular vibrations of molecules. A special type of distribution, proposed earlier [34], contains information not only on dynamics, but on true , or random, breaking of hydrogen bonds. The distributions reveal four different types of characteristic times which reflect different sides of H bond dynamics.