Sofia Kantorovich - Academia.edu (original) (raw)

Papers by Sofia Kantorovich

Physical Review E, 2019

Particle dispersions provide a promising tool for the engineering of functional materials that ex... more Particle dispersions provide a promising tool for the engineering of functional materials that exploit selfassembly of complex structures. Dispersion made from magnetic colloidal particles is a great choice; they are biocompatible and remotely controllable among many other advantages. However, their dominating dipolar interaction typically limits structural complexity to linear arrangements. This paper shows how a magnetostatic equilibrium state with noncollinear arrangement of the magnetic moments, as reported for ferromagnetic Janus particles, enables the controlled self-organization of diverse structures in two dimensions via constant and low-frequency external magnetic fields. Branched clusters of staggered chains, compact clusters, linear chains, and dispersed single particles can be formed and interconverted reversibly in a controlled way. The structural diversity is a consequence of both the inhomogeneity and the spatial extension of the magnetization distribution inside the particles. We draw this conclusion from calculations based on a model of spheres with multiple shifted dipoles. The results demonstrate that fundamentally new possibilities for responsive magnetic materials can arise from interactions between particles with a spatially extended, anisotropic magnetization distribution.

Journal of Magnetism and Magnetic Materials, 2019

Magnetic nanogels represent a cutting edge of magnetic soft matter research due to their numerous... more Magnetic nanogels represent a cutting edge of magnetic soft matter research due to their numerous potential applications. Here, using Langevin dynamics simulations, we analyse the influence of magnetic nanogel concentration and embedded magnetic particle interactions on the self-assembly of magnetic nanogels at zero field. For this, we calculated radial distribution functions and structure factors for nanogels and magnetic particles within them. We found that, in comparison to suspensions of free magnetic nanoparticles, where the self-assembly is already observed if the interparticle interaction strength exceeds the thermal fluctuations by approximately a factor of three, self-assembly of magnetic nanogels only takes place by increasing such ratio above six. This magnetic nanogel self-assembly is realised by means of favourable close contacts between magnetic nanoparticles from different nanogels. It turns out that for high values of interparticle interactions, corresponding to the formation of internal rings in isolated nanogels, in their suspensions larger magnetic particle clusters with lower elastic penalty can be formed by involving different nanogels. Finally, we show that when the self-assembly of these nanogels takes place, it has a drastic effect on the structural properties even if the volume fraction of magnetic nanoparticles is low.

Soft Matter, 2016

We investigate, via a modified mean field approach, the dynamic magnetic response of a polydisper... more We investigate, via a modified mean field approach, the dynamic magnetic response of a polydisperse dipolar suspension to a weak, linearly polarised, AC field. We introduce an additional term into the Fokker-Planck equation, which takes into account dipole-dipole interaction in the form of the first order perturbation, and allows for particle polydispersity. The analytical expressions, obtained for the real and imaginary dynamic susceptibilities, predict three measurable effects: the increase of the real part low-frequency plateaux; the enhanced growth of the imaginary part in the low-frequency range; and the shift of the imaginary part maximum. Our theoretical predictions find an experimental confirmation and explain the changes in the spectrum.

Physical chemistry chemical physics : PCCP, Jan 20, 2016

In the present work we use Langevin dynamics computer simulations to understand how the presence ... more In the present work we use Langevin dynamics computer simulations to understand how the presence of a constant external magnetic field modifies the conformational phase diagram of magnetic filaments in the limit of infinite dilution. We have considered the filaments immersed in either a good (non-sticky filaments) or a poor (Stockmayer polymers) solvent. It has been found that in the presence of an applied field, filaments turn out to be much more susceptible to parameters such as temperature and solvent conditions. Filaments owe this increased susceptibility to the fact that the external magnetic field tends to level the free energy landscape as compared to the zero-field case. The field induces equalization in the free energy of competing conformational states that were separated by large energy differences in the zero-field limit. In this new scenario multistability arises, and manifests itself in the existence of broad regions in the phase diagram where two or more equilibrium c...

Zeitschrift Fur Physikalische Chemie, 2006

In the present paper we compare the static magnetic properties of a bidisperse ferrofluid obtaine... more In the present paper we compare the static magnetic properties of a bidisperse ferrofluid obtained via computer simulations with the predictions of the theoretical chain model. At weak fields, the computer simulations showed a strong dependence of the magnetization on the concentration of large particles. When the latter is small the magnetization behavior is close to the one given by the modified mean field approach, but at higher concentrations of large particles the initial susceptibility increases significantly. This increase cannot be described in terms of the modified mean field model for the homogeneous system. A new theoretical approach for the description of the static magnetic properties of a bidisperse ferrofluid was developed. The theoretical predictions are in good agreement with the results of a recent computer simulation study.

Faraday discussions, Jan 5, 2016

Physical Review E Statistical Nonlinear and Soft Matter Physics, Sep 1, 2009

A combination of analytical calculations and Monte Carlo simulations is used to find the ground s... more A combination of analytical calculations and Monte Carlo simulations is used to find the ground state structures in monodisperse ferrofluid monolayers. Taking into account the magnetic dipole-dipole interaction between all particles in the system we observe different topological structures that are likely to exist at low temperatures. The most energetically favored structures we find are rings, embedded rings, and rings side by side, and we are able to derive analytical expressions for the total energy of these structures. A detailed analysis of embedded rings and rings side by side shows that the interring interactions are negligible. We furthermore find that a single ideal ring is the ground state structure for a ferrofluid monolayer. We compared our theoretical predictions to the results of simulated annealing data and found them to be in excellent agreement.

Magnetohydrodynamics, 2011

We present a generalized version of the itim algorithm for the identification of interfacial mole... more We present a generalized version of the itim algorithm for the identification of interfacial molecules, which is able to treat arbitrarily shaped interfaces. The algorithm exploits the similarities between the concept of probe sphere used in itim and the circumsphere criterion used in the α-shapes approach, and can be regarded either as a reference-frame independent version of the former, or as an extended version of the latter that includes the atomic excluded volume. The new algorithm is applied to compute the intrinsic orientational order parameters of water around a DPC and a cholic acid micelle in aqueous environment, and to the identification of solvent-reachable sites in four model structures for soot. The additional algorithm introduced for the calculation of intrinsic density profiles in arbitrary geometries proved to be extremely useful also for planar interfaces, as it allows to solve the paradox of smeared intrinsic profiles far from the interface.

The Journal of Physical Chemistry B, Oct 31, 2013

We introduce the novel concept of an intrinsic free energy profile, allowing one to remove the ar... more We introduce the novel concept of an intrinsic free energy profile, allowing one to remove the artificial smearing caused by thermal capillary waves, which renders difficulties for the calculation of free energy profiles across fluid interfaces in computer simulations. We apply this concept to the problem of a chloride ion crossing the interface between water and 1,2-dichloroethane and show that the present approach is able to reveal several important features of the free energy profile which are not detected with the usual, nonintrinsic calculations. Thus, in contrast to the nonintrinsic profile, a free energy barrier is found at the aqueous side of the (intrinsic) interface, which is attributed to the formation of a water "finger" the ion pulls with itself upon approaching the organic phase. Further, by the presence of a nonsampled region, the intrinsic free energy profile clearly indicates the coextraction of the first hydration shell water molecules of the ion when entering the organic phase.

Macromolecules, Jan 27, 2015

Faraday Discuss., 2015

We present a theoretical study on the design of a supramolecular magnetoresponsive coating. The c... more We present a theoretical study on the design of a supramolecular magnetoresponsive coating. The coating is formed by a relatively dense array of supracolloidal magnetic filaments grafted to a surface in a polymer brush-like arrangement. In order to determine and optimise the properties of the magnetic filament brush, we perform extensive computer simulations with a coarse-grained model that takes into account the correlations between the magnetic moments of the particles and the backbone crosslinks. We show that the self-assembly of magnetic beads from neighbouring filaments defines the equilibrium structural properties of the complete brush. In order to control this self-assembly, we highlight two external stimuli that can lead to significant effects: temperature of the system and an externally applied magnetic field. Our study reveals self-assembly scenarios inherently driven by the crosslinking and grafting constraints. Finally, we explain the mechanisms of structural changeovers in the magnetic filament brushes and confirm the possibility of controlling them by changing the temperature or the intensity of an external magnetic field.

Macromolecules, 2015

The equilibrium structure of supramolecular magnetic filament brushes is analyzed at two differen... more The equilibrium structure of supramolecular magnetic filament brushes is analyzed at two different scales. First, we study the density and height distributions for brushes with various grafting densities and chain lengths. We use Langevin dynamics simulations with a bead-spring model that takes into account the cross-links between the surface of the ferromagnetic particles, whose magnetization is characterized by a point dipole. Magnetic filament brushes are shown to be more compact near the substrate than nonmagnetic ones, with a bimodal height distribution for large grafting densities. This latter feature makes them also different from brushes with electric dipoles. Next, in order to explain the observed behavior at the filament scale, we introduce a graph theory analysis to elucidate for the first time the structure of the brush at the scale of individual beads. It turns out that, in contrast to nonmagnetic brushes, in which the internal structure is determined by random density fluctuations, magnetic forces introduce a certain order in the system. Because of their highly directional nature, magnetic dipolar interactions prevent some of the random connections to be formed. On the other hand, they favor a higher connectivity of the chains&amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;#39; free and grafted ends. We show that this complex dipolar brush microstructure has a strong impact on the magnetic response of the brush, as any weak applied field has to compete with the dipole-dipole interactions within the crowded environment.

Understanding dielectric spectra can reveal important information about the dynamics of solvents ... more Understanding dielectric spectra can reveal important information about the dynamics of solvents and solutes from the dipolar relaxation times down to electronic ones. In the late 1970s, Hubbard and Onsager predicted that adding salt ions to a polar solution would result in a reduced dielectric permittivity that arises from the unexpected tendency of solvent dipoles to align opposite to the applied field. So far, this effect has escaped an experimental verification, mainly because of the concomitant appearance of dielectric saturation from which the Hubbard-Onsager decrement cannot be easily separated. Here we develop a novel non-equilibrium molecular dynamics simulation approach to determine this decrement accurately for the first time. Using a thermodynamic consistent all-atom force field we show that for an aqueous solution containing sodium chloride around 4.8 Mol/l, this effect accounts for 12\% of the total dielectric permittivity. The dielectric decrement can be strikingly di...

With the help of a recently developed non-equilibrium approach, we investigate the ionic strength... more With the help of a recently developed non-equilibrium approach, we investigate the ionic strength dependence of the Hubbard--Onsager dielectric decrement. We compute the depolarization of water molecules caused by the motion of ions in sodium chloride solutions from the dilute regime (0.035 M) up close to the saturation concentration (4.24 M), and find that the kinetic decrement displays a strong nonmonotonic behavior, in contrast to the prediction of available models. We introduce a modification of the Hubbard--Onsager continuum theory, that takes into account the screening due to the ionic cloud at mean field level, and, is able to predict quantitatively the value of the kinetic decrement in the whole inspected range.

Journal of Physics: Condensed Matter, 2015

We present a theoretical study of Janus-like magnetic particles at low temperature. To describe t... more We present a theoretical study of Janus-like magnetic particles at low temperature. To describe the basic features of the Janus-type magnetic colloids, we put forward a simple model of a spherical particle with a dipole moment shifted outwards from the centre and oriented perpendicular to the particle radius. Using direct calculations and molecular dynamics computer simulations, we investigate the ground states of small clusters and the behaviour of bigger systems at low temperature. In both cases the important parameter is the dipolar shift, which leads to different ground states and, as a consequence, to a different microscopic behaviour in the situation when the thermal fluctuations are finite. We show that the head-to-tail orientation of dipoles provides a two-particle energy minima only if the dipoles are not shifted from the particle centres. This is one of the key differences from the system of shifted dipolar particles (sd-particles), in which the dipole was shifted outwards radially, studied earlier (Kantorovich et al 2011 Soft Matter 7 5217-27). For sd-particles the dipole could be shifted out of the centre for almost 40% before the head-to-tail orientation was losing its energetic advantage. This peculiarity manifests itself in the topology of the small clusters in the ground state and in the response of the Janus-like particle systems to an external magnetic field at finite temperatures.

Journal of Magnetism and Magnetic Materials, 2015

Nanoscale, 2015

To design modern materials with a specific response, the consequences of directionally dependent ... more To design modern materials with a specific response, the consequences of directionally dependent interactions on the self-assembly of constituent nanoparticles need to be properly understood. Directionality arises in the study of anisometric nanoparticles, where geometry has a drastic effect on the properties observed. Given the fact that magnetic interactions are inherently anisotropic, if one constructs these particles from a magnetic medium, an interesting interplay between the two sources of directionality will occur. We have investigated this scenario by exploring systems of dipolar nanocube monolayers. Using an applied analytical approach, in combination with molecular dynamics simulations, we have determined the ground state structures of individual monolayer clusters. Taking inspiration from experiments, two different fixed dipole orientations for the permanent magnetisation of the nanocubes were considered: the first aligned along the [001] crystallographic axis of each cube, and the second along the [111] axis. We discovered that the structure of the ground state is distinctly different for the two systems of permanently magnetised nanocubes; [001] cubes form dipolar chains in the ground state, whereas those with [111] orientation adopt square lattice structures. The discovered configurations in the ground state represent two different structural motifs, as yet unobserved in the ground state of other magnetic nanoparticle systems.