88 research outputs found
How chains and rings affect the dynamic magnetic susceptibility of a highly clustered ferrofluid
The dynamic magnetic susceptibility, χ(ω), of a model ferrofluid at a very low concentration (volume fraction, approximately 0.05%), and with a range of dipolar coupling constants (1≤λ≤8), is examined using Brownian dynamics simulations. With increasing λ, the structural motifs in the system change from unclustered particles, through chains, to rings. This gives rise to a nonmonotonic dependence of the static susceptibility χ(0) on λ and qualitative changes to the frequency spectrum. The behavior of χ(0) is already understood, and the simulation results are compared to an existing theory. The single-particle rotational dynamics are characterized by the Brownian time, τB, which depends on the particle size, carrier-liquid viscosity, and temperature. With λ≤5.5, the imaginary part of the spectrum, χ′′(ω), shows a single peak near ω∼τB-1, characteristic of single particles. With λ≥5.75, the spectrum is dominated by the low-frequency response of chains. With λ≥7, new features appear at high frequency, which correspond to intracluster motions of dipoles within chains and rings. The peak frequency corresponding to these intracluster motions can be computed accurately using a simple theory. © 2021 American Physical Society.A.O.I. gratefully acknowledges research funding from the Ministry of Science and Higher Education of the Russian Federation (Ural Mathematical Center Project No. 075-02-2021-1387)
Effects of nanoparticle heating on the structure of a concentrated aqueous salt solution
The effects of a rapidly heated nanoparticle on the structure of a concentrated aqueous salt solution are studied using molecular dynamics simulations. A diamond-like nanoparticle of radius 20 Å is immersed in a sodium-chloride solution at 20% above the experimental saturation concentration and equilibrated at T = 293 K and P = 1 atm. The nanoparticle is then rapidly heated to several thousand degrees Kelvin, and the system is held under isobaric-isoenthalpic conditions. It is observed that after 2-3 ns, the salt ions are depleted far more than water molecules from a proximal zone 15-25 Å from the nanoparticle surface. This leads to a transient reduction in molality in the proximal zone and an increase in ion clustering in the distal zone. At longer times, ions begin to diffuse back into the proximal zone. It is speculated that the formation of proximal and distal zones, and the increase in ion clustering, plays a role in the mechanism of nonphotochemical laser-induced nucleation. © 2017 Author(s)
Influence of dipolar interactions on the magnetic susceptibility spectra of ferrofluids
The frequency-dependent magnetic susceptibility of a ferrofluid is calculated under the assumption that the constituent particles undergo Brownian relaxation only. Brownian-dynamics simulations are carried out in order to test the predictions of a recent theory [A. O. Ivanov, V. S. Zverev, and S. S. Kantorovich, Soft Matter 12, 3507 (2016)1744-683X10.1039/C5SM02679B] that includes the effects of interparticle dipole-dipole interactions. The theory is based on the so-called modified mean-field approach and possesses the following important characteristics: in the low-concentration, noninteracting regime, it gives the correct single-particle Debye-theory results; it yields the exact leading-order results in the zero-frequency limit; it includes particle polydispersity correctly from the outset; and it is based on firm theoretical foundations allowing, in principle, systematic extensions to treat stronger interactions and/or higher concentrations. The theory and simulations are compared in the case of a model monodisperse ferrofluid, where the effects of interactions are predicted to be more pronounced than in a polydisperse ferrofluid. The susceptibility spectra are analyzed in detail in terms of the low-frequency behavior, the position of the peak in the imaginary (out-of-phase) part, and the characteristic decay time of the magnetization autocorrelation function. It is demonstrated that the theory correctly predicts the trends in all of these properties with increasing concentration and dipolar coupling constant, the product of which is proportional to the Langevin susceptibility χL. The theory is in quantitative agreement with the simulation results as long as χL1. © 2016 American Physical Society
The influence of interparticle correlations and self-assembly on the dynamic initial magnetic susceptibility spectra of ferrofluids
Using computer simulations and a mean-field theoretical approach, we study how the growth in dipolar interparticle correlations manifests itself in the frequency-dependent initial magnetic susceptibility of a ferrofluid. Our recently developed theory gives the correct single-particle Debye-theory results in the low-concentration, non-interacting regime; and it yields the exact leading-order contributions from interparticle correlations. The susceptibility spectra are analysed in terms of the low-frequency behaviours of the real and imaginary parts, and the position of the peak in the imaginary part. By comparing the theoretical predictions to the results from Brownian dynamics simulations, it is possible to identify the conditions where correlations are important, but where self-assembly has not developed. We also provide a qualitative explanation for the behaviour of spectra beyond the mean-field limit. © 2016 Elsevier B.V
First-Principles Study on Ligand Binding and Positional Disorder in Pentlandite
Density
functional theory, in conjunction with a cluster expansion
model, has been used to study the structure and stability of the positionally
disordered iron–nickel sulfide mineral pentlandite (Pn), (Fe,Ni)<sub>9</sub>S<sub>8</sub>, with results indicating heterogeneous nearest
neighbor metal contacts are more energetically favorable than homogeneous
contacts. The virtual crystal approximation was also explored as a
means to address positional disorder, but while reliable results could
be obtained for the bulk model, the same was not true for the surface,
as local distortions which affected the surface model energies could
not be reproduced. We also address the binding of ethyl xanthate (CH<sub>3</sub>CH<sub>2</sub>OCS<sub>2</sub><sup>–</sup>), water,
and hydroxide to the [111] Pn surface to understand the mode of action
of industrial xanthate flotation agents better. In order to model
anionic ligands bound to a periodic boundary condition surface we
propose applying a correction derived from the surface work function
to remove the additional charge introduced by the ligand. The results
obtained from the ligand binding studies indicate that while ethyl
xanthate could readily displace up to a full monolayer of water per
unit cell it is likely that Fe-enriched surfaces will bind xanthate
in competition with the hydroxide anion, while a Ni-enriched surface
will preferentially bind hydroxide anions over xanthate
Disordered Filaments Mediate the Fibrillogenesis of Type I Collagen in Solution
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Thermodynamics of the Stockmayer fluid in an applied field
The thermodynamic properties of the Stockmayer fluid in an applied field are studied using theory and computer simulation. Theoretical expressions for the second and third virial coefficients are obtained in terms of the dipolar coupling constant (, measuring the strength of dipolar interactions as compared to thermal energy) and dipole-field interaction energy (α, being proportional to the applied field strength). These expressions are tested against numerical results obtained by Mayer sampling calculations. The expression for the second virial coefficient contains terms up to λ4, and is found to be accurate over realistic ranges of dipole moment and temperature, and over the entire range of the applied field strength (from zero to infinity). The corresponding expression for the third virial coefficient is truncated at λ3, and is not very accurate: higher order terms are very difficult to calculate. The virial coefficients are incorporated in to a thermodynamic theory based on a logarithmic representation of the Helmholtz free energy. This theory is designed to retain the input virial coefficients, and account for some higher order terms in the sense of a resummation. The compressibility factor is obtained from the theory and compared to results from molecular dynamics simulations with a typical value λ = 1. Despite the mathematical approximations of the virial coefficients, the theory captures the effects of the applied field very well. Finally, the vapour-liquid critical parameters are determined from the theory, and compared to published simulation results; the agreement between the theory and simulations is good. © 2015 Taylor & Francis
Static magnetization of immobilized, weakly interacting, superparamagnetic nanoparticles
The magnetization curve and initial susceptibility of immobilized superparamagnetic nanoparticles are studied using statistical-mechanical theory and Monte Carlo computer simulations. The nanoparticles are considered to be distributed randomly within an implicit solid matrix, but with the easy axes distributed according to particular textures: these are aligned parallel or perpendicular to an external magnetic field, or randomly distributed. The magnetic properties are calculated as functions of the magnetic crystallographic anisotropy barrier (measured with respect to the thermal energy by a parameter σ), and the Langevin susceptibility (related to the dipolar coupling constant and the volume fraction). It is shown that the initial susceptibility χ is independent of σ in the random case, an increasing function of σ in the parallel case, and a decreasing function of σ in the perpendicular case. Including particle-particle interactions enhances χ, and especially so in the parallel case. A first-order modified mean-field (MMF1) theory is accurate as compared to the simulation results, except in the parallel case with a large value of σ. These observations can be explained in terms of the range and strength of the (effective) interactions and correlations between particles, and the effects of the orientational degrees of freedom. The full magnetization curves show that a parallel texture enhances the magnetization, while a perpendicular texture suppresses it, with the effects growing with increasing σ. In the random case, while the initial response is independent of σ, the high-field magnetization decreases with increasing σ. These trends can be explained by the energy required to rotate the magnetic moments with respect to the easy axes. © 2019 The Royal Society of Chemistry.Ministry of Science and Higher Education of the Russian Federation: 02.A. O. I. and E. A. E. gratefully acknowledge research funding from the Ministry of Science and Higher Education of the Russian Federation (Contract No. 02.A03.21.006, Project No. 3.1438.2017/4.6)
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