Combining nuclear magnetic resonance and molecular dynamics simulations, we unravel the long-time dynamics of a paradigmatic colloid with strong dipole-dipole interactions. In a homogeneous magnetic field, ionic ferrofluids exhibit a stepwise association process from ensembles of monomers over stringlike chains to bundles of hexagonal zipped-chain patches. We demonstrate that attractive van der Waals interactions due to charge-density fluctuations in the magnetic particles play the key role for the dynamical stabilization of the hexagonal superstructures against thermal dissociation. Our results give insight into the dynamics of self-organization in systems dominated by dipolar interactions.

We investigate the spatiotemporal distribution of microscopic relaxation events, defined through particle hops, in a model polymer glass using molecular dynamics simulations. We introduce an efficient algorithm to directly identify hops during the simulation, which allows the creation of a map of relaxation events for the whole system. Based on this map, we present density-density correlations between hops and directly extract correlation scales. These scales define collaboratively rearranging groups of particles and their size distributions are presented as a function of temperature and age. Dynamical heterogeneity is spatially resolved as the aggregation of hops into clusters, and we analyze their volume distribution and growth during aging. A direct comparison with the four-point dynamical susceptibility χ(4) reveals the formation of a single dominating cluster prior to the χ(4) peak, which indicates maximally correlated dynamics. An analysis of the fractal dimension of the hop clusters finds slightly noncompact shapes in excellent agreement with independent estimates from four-point correlations.

We present a quantitative analysis of the correlation between quasi-localized, low energy vibrational modes and structural relaxation events in computer simulations of a quiescent, thermal polymer glass. Our results extend previous studies on glass forming binary mixtures in 2D, and show that the soft modes identify regions that undergo irreversible rearrangements with up to 7 times the average probability. We study systems in the supercooled- and aging-regimes and discuss temperature- as well as age-dependence of the correlation. In addition to the location of rearrangements, we find that soft modes also predict their direction on the molecular level. The soft regions are long lived structural features, and the observed correlations vanish only after >50% of the system has undergone rearrangements.

Molecular dynamics simulations of a coarse-grained model of a polymer glass were used to study the recovery regime following deformation at constant stress or constant strain rate. We monitor dynamical as well as structural and energetic quantities to characterize the impact of deformation on the relaxation process. The α-relaxation times are reduced relative to an unperturbed sample immediately after deformation, and we observe a gradually increasing "erasure" of memory with increasing amount of deformation. Remarkably, the single deformation parameter that captures this continuous transition is the total strain at the end of deformation. For deformation up to of order the yield strain, the evolution of multiple measures of short-range order and the inherent structure energy closely track changes of the αrelaxation time, suggesting that the "rejuvenated" state is close to that of a younger glass. For larger strains accessible by constant strain rate deformation, however, plastic yield generates a distinctly different thermodynamic state.

aWe have used low-field 1 H nuclear-magnetic resonance (NMR) spectroscopy and molecular dynamics (MD) to investigate the aggregation dynamics of magnetic particles in ionic ferrofluids (IFFs) in the presence of magnetic field gradients. At the beginning of the experiments, the measured NMR spectra were broad and asymmetric, exhibiting two features attributed to different dynamical environments of water protons, depending on the local strength of the field gradients. Hence, the spatial redistribution of the magnetic particles in the ferrofluid caused by the presence of an external magnetic field in a time scale of minutes can be monitored in real time, following the changes in the features of the NMR spectra during a period of about an hour. As previously reported [Heinrich et al., Phys. Rev. Lett., 2011, 106, 208301], in the homogeneous magnetic field of a NMR spectrometer, the aggregation of the particles of the IFF proceeds in two stages. The first stage corresponds to the gradual aggregation of monomers prior to and during the formation of chain-like structures. The second stage proceeds after the chains have reached a critical average length, favoring lateral association of the strings into hexagonal zipped-chain superstructures or bundles. In this work, we focus on the influence of a strongly inhomogeneous magnetic field on the aforementioned aggregation dynamics. The main observation is that, as the sample is immersed in a certain magnetic field gradient and kept there for a time t inh , magnetophoresis rapidly converts the ferrofluid into an aggregation state which finds its correspondence to a state on the evolution curve of the pristine sample in a homogeneous field. From the degree of aggregation reached at the time t inh , the IFF sample just evolves thereafter in the homogeneous field of the NMR spectrometer in exactly the same way as the pristine sample. The final equilibrium state always consists of a colloidal suspension of zipped-chain bundles with the chain axes aligned along the magnetic field direction.