Collective Effects on Single Particle Orientational Relaxation in Slow Dipolar Liquids

Theoretical and computer simulation studies of orientational relaxation in dense molecular liquids are presented. The emphasis of the study is to understand the effects of collective orientational relaxation on the single-particle orientational dynamics. The theoretical analysis is based on a recently developed molecular hydrodynamic theory which allows a self-consistent description of both the collective and the single-particle orientational relaxation. The molecular hydrodynamic theory can be used to derive a relation between the memory function for the collective orientational correlation function and the frequency-dependent dielectric function. A novel feature of the present work is the demonstration that this collective memory function is significantly different from the single-particle rotational friction. However, a microscopic expression for the single-particle rotational friction can be derived from the molecular hydrodynamic theory where the collective memory function can be used to obtain the single-particle orientational friction. This procedure allows, us to calculate the single-particle orientational correlation function near the alpha-beta transition in the supercooled liquid. The calculated correlation function shows an interesting bimodal decay below the bifurcation temperature as the glass transition is approached from above. Brownian dynamics simulations have been carried out to check the validity of the above procedure of translating the memory function from the dielectric relaxation data. We have also investigated the following two issues important in understanding the orientational relaxation in slow liquids. First, we present an analysis of the ''orientational caging'' of translational motion. The value of the translational friction is found to be altered significantly by the orientational caging. Second, we address the question of the rank dependence of the dielectric friction using both simulation and the molecular hydrodynamic theory.

Molecular hydrodynamic theory of non‐Markovian collective orientational relaxation in dense dipolar liquids

A microscopic study of the non‐Markovian (or memory) effects on the collective orientational relaxation in a dense dipolar liquid is carried out by using an extended hydrodynamic approach which provides a reliable description of the dynamical processes occuring at the molecular length scales. Detailed calculations of the wave‐vector dependent orientational correlation functions are presented. The memory effects are found to play an important role; the non‐Markovian results differ considerably from that of the Markovian theory. In particular, a slow long‐time decay of the longitudinal orientational correlation function is observed for dense liquids which becomes weaker in the presence of a sizeable translational contribution to the collective orientational relaxation. This slow decay can be attributed to the intermolecular correlations at the molecular length scales. The longitudinal component of the orientational correlation function becomes oscillatory in the underdamped limit of momenta relaxations and the frequency dependence of the friction reduce the frictional resistance on the collective excitations (commonly known as dipolarons) to make them long lived. The theory predicts that these dipolarons can, therefore, be important in chemical relaxation processes, in contradiction to the claims of some earlier theoretical studies.

Evidence of collective relaxation behavior in the reentrant phase of oxygen-rich LaMnO3

The reentrant low temperature phase of the perovskite manganite LaMnO3+delta (delta=0.22) has been investigated with ac susceptibility and dc magnetization studies. A critical examination of the memory effects in ac susceptibility leads us to the conclusion that the slow dynamics in the system is a consequence of collective relaxation processes resulting from interactions between ferromagnetic clusters, whose presence was indicated in earlier studies. Here, we postulate that the collective behavior is due to the existence of long-range (dipolar) interactions between the large ferromagnetic `superspins'. This is also confirmed by an abnormally large microscopic spin-flip time (similar to 10(-9) s) compared to a canonical spin glass. (C) 2013 Elsevier B.V. All rights reserved.

Organization dependent collective magnetic properties of secondary nanostructures with differential spatial ordering and magnetic easy axis orientation

Achieving control on the formation of different organization states of magnetic nanoparticles is crucial to harness their organization dependent physical properties in desired ways. In this study, three organization states of iron oxide nanoparticles (gamma-Fe2O3), defining as (i) assembly (ii) network aggregate and (iii) cluster, have been developed by simply changing the solvent evaporation conditions. All three systems have retained the same phase and polydispersity of primary particles. Magnetic measurements show that the partial alignment of the easy axes of the particles in the network system due to the stacking aggregation morphology can result in significant enhancement of the coercivity and remanence values, while the opposite is obtained for the cluster system due to the random orientation of easy axes. Partial alignment in the aggregate system also results in noticeable non -monotonic field dependence of ZFC peak temperature (TpeaB). The lowest value of the blocking temperature (TB) for the cluster system is related to the lowering of the effective anisotropy due to the strongest demagnetizing effect. FC (Field cooled) memory effect was observed to be decreasing with the increasing strength of dipolar interaction of organization states. Therefore, the stacking aggregation and the cluster formation are two interesting ways of magnetic nanoparticles organization for modulating collective magnetic properties significantly, which can have renewed application potentials from recording devices to biomedicine. (C) 2016 Elsevier B.V. All rights reserved.