S. Corezzi

Connecting Irreversible to Reversible Aggregation: Time and Temperature

We report molecular dynamics simulations of a gel-forming mixture of ellipsoidal patchy particles with different functionality. We show that in this model, which disfavors the formation of bond-loops, elapsed time during irreversible aggregation--leading to the formation of an extended network--can be formally correlated with equilibrium temperature in reversible aggregation. We also show that it is possible to develop a parameter-free description of the self-assembly kinetics, bringing reversible and irreversible aggregation of loopless branched systems to the same level of understanding as equilibrium polymerization.

Chemical and physical aggregation of small-functionality particles

The number of potentially relevant materials resulting from the aggregation of elementary units with a finite functionality continues to increase. The growth of branched clusters and networks may proceed through the formation of reversible (physical) or irreversible (chemical) bonds. The kinetics of bond formation is sensitive both to the intrinsic rate of the bonding process, controlled by the chemistry of the system, and to the encounter rate of clusters, controlled by cluster diffusion. In this Highlight we review a series of our recent numerical simulation studies designed to investigate the connections between chemical and physical aggregation and the crossover from a chemically controlled to diffusion-controlled regime. It is shown that in the chemically controlled limit, it is possible to formally correlate elapsed time during irreversible aggregation with equilibrium temperature in reversible aggregation. The diffusion-controlled regime sets in well-beyond percolation and the effect of diffusion can be described by introducing a single additional time scale, related to the average diffusion time. This concept can be readily generalized to interpret the experimental data.

Slow dynamics of salol: a pressure- and temperature-dependent light scattering study.

We study the slow dynamics of salol by varying both temperature and pressure using photon correlation spectroscopy and pressure-volume-temperature measurements, and compare the behavior of the structural relaxation time with equations derived within the Adam-Gibbs entropy theory and the Cohen-Grest free volume theory. We find that pressure-dependent data are crucial to assess the validity of these model equations. Our analysis supports the entropy-based equation, and estimates the configurational entropy of salol at ambient pressure approximately 70% of the excess entropy. Finally, we investigate the evolution of the shape of the structural relaxation process, and find that a time-temperature-pressure superposition principle holds over the range investigated.

Hydrophobic Hydration in Water-tert-Butyl Alcohol Solutions by Extended Depolarized Light Scattering.

Molecular dynamics and structural properties of water-tert-butyl alcohol (TBA) mixtures are studied as a function of concentration by extended depolarized light scattering (EDLS) experiments. The wide frequency range, going from fraction to several thousand GHz, explored by EDLS allows distinguishing TBA rotational dynamics from structural relaxation of water and intermolecular vibrational and librational modes of the solution. Contributions to the water relaxation originating from two distinct populations, i.e. hydration and bulk water, are clearly identified. The dynamic retardation factor of hydration water with respect to the bulk, ξ ≈ 4, almost concentration independent, is one of the smallest found by EDLS among a variety of systems of different nature and complexity. This result, together with the small number of water molecules perturbed by the presence of TBA, supports the idea that hydrophobic simple molecules are less effective than hydrophilic and more complex molecules in perturbing the H-bond network of liquid water. At increasing TBA concentrations the average number of perturbed water molecules shows a pronounced decrease and the characteristic frequency of librational motions reduces significantly, both of which are results consistent with the occurrence of self-aggregation of TBA molecules.

Clustering, glass transition and gelation in a reactive fluid

We study the dependence of the dynamics on the size of particle clusters that grow by stepwise aggregation in a two-component reactive mixture. The data reveal the cluster property involved in the glasslike arrest and its quantitative link with the structural relaxation time. Specifically, we measured the number-average cluster size xn—i.e., the average number of bonded monomers per molecule—and, independently, the characteristic time τ for decay of the photon correlation function, throughout the reaction. We find that xn diverges as the system freezes at the glass transition, xn and τ being exponentially related. The comparison with the gel transition that occurs at the divergence of the weight-average cluster size provides evidence that the two transitions are associated to distinct properties of the same underlying clustering process.

Hydration and rotational diffusion of levoglucosan in aqueous solutions

Extended frequency range depolarized light scattering measurements of water-levoglucosan solutions are reported at different concentrations and temperatures to assess the effect of the presence and distribution of hydroxyl groups on the dynamics of hydration water. The anhydro bridge, reducing from five to three the number of hydroxyl groups with respect to glucose, considerably affects the hydration properties of levoglucosan with respect to those of mono and disaccharides. In particular, we find that the average retardation of water dynamics is ≈3-4, that is lower than ≈5-6 previously found in glucose, fructose, trehalose, and sucrose. Conversely, the average number of retarded water molecules around levoglucosan is 24, almost double that found in water-glucose mixtures. These results suggest that the ability of sugar molecules to form H-bonds through hydroxyl groups with surrounding water, while producing a more effective retardation, it drastically reduces the spatial extent of the perturbation on the H-bond network. In addition, the analysis of the concentration dependence of the hydration number reveals the aptitude of levoglucosan to produce large aggregates in solution. The analysis of shear viscosity and rotational diffusion time suggests a very short lifetime for these aggregates, typically faster than ≈20 ps.

On the interplay between the slowdown of dynamics and the kinetics of aggregation: The case study of a reactive binary mixture

Modeling the kinetics of aggregation requires a proper strategy to take into account not only the reactivity of reagents but also the ability they have to diffuse. The lack of direct information about diffusion represents the most serious experimental obstacle to the use of diffusion-corrected mean-field equations, which is usually overcome by using information on the structural relaxation dynamics. A very accurate description of the entire kinetics of aggregation can be made by introducing a single time scale of diffusion, set by the structural relaxation time τ of the system according to ∼τ(ξ), with ξ a fractional exponent. Here, we apply this modeling to the case of a reactive binary mixture made of diglycidyl ether of bisphenol-A and 1,3-phenylenediamine, where the reaction proceeds along an autocatalyic (hydroxyl catalyzed) and a non-catalytic (impurity catalyzed) pathway and find that a very small value of the exponent ξ = 0.27 ± 0.03 is needed to reproduce all the data. Our results help revise some preconceived ideas: contrary to widely held assumptions, we find that (i) the time scale of diffusion neither increases proportionally to the structural relaxation time nor is related to τ by a power law with the same fractional exponent as that relating τ to conductivity; (ii) no direct connection exists between the transition to diffusion-control and the development of a gel network or formation of a glassy phase; and (iii) there is no significant difference in the enthalpy barrier for bond formation in the presence of hydroxyl or other than hydroxyl catalyst groups.