偶极流体的理论研究

铁电液晶、磁流体等在现代功能材料中具有重要地位,对人们的现实生活也产生了深远影响.本文着力介绍包含球形粒子的偶极流体体系在没有外场情况下的一些结构和性质,以及偶极相互作用对该体系的影响.介绍了国外研究偶极流体所采用的最新方法,这有助于我们进一步了解偶极流体复杂的结构和相变性质.     

Long-range correction for dipolar fluids at planar interfaces

A slab-based long-range correction for dipolar interactions in molecular dynamics simulation of systems with a planar geometry is presented and applied to simulate vapour–liquid interfaces. The present approach is validated with respect to the saturated liquid density and the surface tension of the Stockmayer fluid and a molecular model for ethylene oxide. The simulation results exhibit no dependence on the cut-off radius for radii down to 1 nm, proving that the long-range correction accurately captures the influence of the dipole moment on the intermolecular interaction energies and forces as well as the virial and the surface tension.     

Thermodynamics of pure and multicomponent dipolar hard-sphere fluids

The thermodynamics of two recent models of hard-sphere polar fluids is investigated. The two models are the Onsager model developed by Nienhuis and Deutch and the mean spherical approximation results obtained by Wertheim. The equation of state, vapour pressure curve, and other pertinent thermodynamic properties are determined. These results for the pure hard-sphere polar fluid complement the results recently reported by Rushbrooke, Stell and Høye. The thermodynamics of simple multicomponent hard-sphere polar mixtures is examined for the case of equal hard-sphere radii. Results for the multicomponent MSM are based on the exact solution of this model by Adelman and Deutch. The Onsager model is generalized to the case of many components. For both multicomponent models it is demonstrated that a variety of regions of instability exist for the one-phase fluid. Finally a discussion is included of how well these models agree with experiment.     

Phase transitions and ordering of confined dipolar fluids

We apply a modified mean-field density functional theory to determine the phase behavior of Stockmayer fluids in slit-like pores formed by two walls with identical substrate potentials. Based on the Carnahan-Starling equation of state, a fundamental-measure theory is employed to incorporate the effects of short-ranged hard-sphere-like correlations while the long-ranged contributions to the fluid interaction potential are treated perturbatively. The liquid-vapor, ferromagnetic-liquid-vapor, and ferromagnetic-liquid-isotropic-liquid first-order phase separations are investigated. The local orientational structure of the anisotropic and inhomogeneous ferromagnetic liquid phase is also studied. We discuss how the phase diagrams are shifted and distorted upon varying the pore width.     

An equation of state contribution for dipolar and quadrupolar square-well fluids

A dipolar–quadrupolar contribution to the residual Helmholtz energy for a polar square well (a square well plus either a point dipole or a point quadrupole) fluid is developed based on the Padé approximation. Taking the square well system as reference, the contribution is formulated using an expansion for radial distribution function of the reference system. In addition to square well potential parameters the contribution depends only on dipole and quadrupole moments. This term is added as perturbation to a generalized equation of state for square well fluids. The results are then compared with the available simulation data in the literature. With the new equation obtained, it was possible to predict liquid–vapour equilibrium properties and critical properties of polar square well fluids more accurately than with available perturbation theories for multipolar square well systems. Application of the equation of state to a real dipolar (water) and a real quadrupolar (carbon dioxide) fluid indicated that the polar contribution greatly improved the predictions of saturation properties. Accurate prediction of critical properties for polar square well fluids remains as a challenge. This work can be useful in the development of better equations of state.     

Molecular dynamics simulations of a silver atom in water: evidence for a dipolar excitonic state

The properties of a silver atom in bulk water were studied for the first time by molecular dynamics simulations using two complementary mixed quantum-classical approaches. The first one consists of treating by quantum mechanics one electron only, which interacts with a classical silver cation and solvent through one-electron pseudopotentials. The second one is Car-Parrinello molecular dynamics that treats all the valence electrons quantum-mechanically. Very good agreement is obtained between these two methods, and the calculated absorption spectrum of the solvated silver atom agrees very well with experimental data. Both simulations reveal that the silver atom is in the critical region for the appearance of a dipolar excitonic state and exhibits a dipole moment of approximately 2 D with large fluctuations of +/-1 D. The structure of the solvation shell is also analyzed.     

Exchange and dipolar interactions in solid organic radicals

Investigations of the E.S.R. linewidths of exchange narrowed lines from solid organic free radicals allow one to obtain information about both the exchange interaction and the electron-electron dipolar interaction in some instances. In cases in which the dipolar interaction is incompletely averaged by spin exchange one can use the frequency dependence of the E.S.R. linewidth to determine the magnitudes of the exchange frequency and the dipolar interaction. This paper reports results from a study of the frequency and temperature dependence of the linewidth of four solid organic radicals. The dipole-dipole interaction of the two nitroxide radicals included in this study was found to be temperature dependent, indicating changes in intermolecular spin separation with temperature. The exchange energy of these two radicals appeared to vary exponentially with the separation of the spins through most of the temperature interval which was investigated.     

Coupling of ferromagnetic nanoparticles through dipolar interactions

We consider two ferromagnetic nanoparticles coupled via long-range dipolar interactions. We model each particle by a three-dimensional array of classical spin vectors, with a central spin surrounded by a variable number of shells. Within each particle only ferromagnetic coupling between nearest neighbor spins is considered. The interaction between particles is of the dipolar type and the magnetic properties of the system is studied as a function of temperature and distance between the centers of the particles. We perform Monte Carlo simulations for particles with different number of shells, and the magnetic properties are calculated via two routes concerning the dipolar contribution: one assuming a mean-field like coupling between effective magnetic moments at the center of the particles, and other one, where we take into account interactions among all the pairs of spins, one in each particle. We show that the dipolar coupling between the particles enhances the critical temperature of the system relative to the case in which the particles are very far apart. The dipolar energy between the particles is smaller when the assumption of effective magnetic moment of the particles is used in the calculations.     

Coherent control and polarization readout of individual excitonic states

We present measurements and simulations of coherent control and readout of the polarization in individual exciton states. The readout is accomplished by transient four-wave mixing detected by heterodyne spectral interferometry. We observe Rabi oscillations in the polarization, which show half the period of the Rabi oscillations in the population. A decrease of the oscillation amplitude with pulse area is observed, which is not accompanied by a change in the dephasing time. This suggests the transfer of the excitation to other states as the origin of the Rabi-oscillation damping. Detuning of the excitation enables the control of the polarization in phase and amplitude and is in qualitative agreement with simulations for a two-level system. Additionally, simultaneous Rabi flopping of several spatially and energetically close exciton states is demonstrated.     

Cluster expansion for fluids with long-range interactions

We apply Kac's method of functional integration to a spatially non-uniform fluid with short and long-range interactions. The system with short-range interactions is treated as a reference system to which the long-range pair interaction is added as a perturbation. All equilibrium distribution functions of the reference system are assumed known. We show by diagram analysis that by a suitable choice of the density profile of the reference system the thermodynamic potential can be expressed in terms of a cluster expansion containing only irreducible diagrams. For a spatially uniform fluid in the thermodynamic limit our results reduce to those obtained by Siegert et al.     

Critical behavior of uniaxial ferromagnetics with dipolar interactions

The critical behavior of uniaxial ferromagnets with exchange and dipolar interaction is studied by exact renormalization group techniques. A crossover occurs from short-range (Ising) to characteristic dipolar behavior, which is described.     

Comparing contact and dipolar interactions in a Bose-Einstein condensate

We have measured the relative strength epsilon dd of the magnetic dipole-dipole interaction compared with the contact interaction in a dipolar chromium Bose-Einstein condensate. We analyze the asymptotic velocities of expansion of the condensate with different orientations of the atomic magnetic moments. By comparing the experimental results with numerical solutions of the hydrodynamic equations for dipolar condensates, we obtain epsilon dd = 0.159+/-0.034. We use this result to determine the s-wave scattering length a = (5.08+/-1.06 x 10(-9)) m = (96+/-20) a0 of 52Cr. This is fully consistent with our previous measurements on the basis of Feshbach resonances and therefore confirms the validity of the theoretical approach used to describe the dipolar Bose-Einstein condensate.     

Aggregation kinetics and the nature of phase separation in two-dimensional dipolar fluids

The kinetics of aggregation in a monolayer of dipolar particles are studied using stochastic dynamics computer simulations. Transient concentrations of end defects (at low density) and Y-shaped defects (at high density) clearly exceed those at equilibrium. Although very large dipole moments are expected to disfavor such defects at equilibrium, it is found that the transient defect concentrations increase with increasing dipole moment. The results suggest that the conditions for defect-driven condensation--as proposed by Tlusty and Safran [T. Tlusty and S. A. Safran, Science 290, 1328 (2000)]--could be met by kinetic trapping, giving rise to a metastable phase transition between isotropic fluid phases.     

The role of dipolar interactions for the magnetic properties of ferromagnetic nanoring

We investigate numerically the effects of the dipolar interactions on magnetic properties in small ferromagnetic nanorings using a Monte Carlo technique. Our simulated results show that the strength of dipolar interaction in the magnetic nanoring has an important influence on the magnetization reversal processes and further the coercivity and the remanence. As the dipolar interaction increases, the transition of magnetization reversal processes from the onion-rotation state to the vortex state can occur, which results in an increase in coercivity and a decrease in remanence. On the other hand, it is found that the coercivity and the remanence depend more strongly on the strength of dipolar coupling for the relatively small size nanoring than for the large size nanoring in width. This can be attributed to the stable vortex state without core in smaller width nanoring in contrast to the metastable vortex state with core in larger width nanoring, induced by strong dipolar interactions. Additionally, the temperature dependence of coercivity and remanence in magnetic nanoring is also studied at a fixed dipolar interaction.     

Variational principle for flow of non-Newtonian fluids

A variational principle is formulated for finding stationary solutions of the equations of motion for an incompressible non-Newtonian fluid with constitutive equation of the Reiner-Rivlin type. The basic functional is related, but not identical to the rate of energy dissipation. It can be used for analyzing the stability of the stationary state against small perturbations.     

Spin relaxation of positive muons due to dipolar interactions

The time dependence of the polarization function for a static muon interacting with nuclear spins is investigated, and deviations from the results of the Kubo-Toyabe theory are found. The corresponding modifications for dynamical relaxation functions are exhibited, and the effect of quantum-mechanical correlations on the spin dynamics is pointed out.     

Magnetization of nanomagnet assemblies: Effects of anisotropy and dipolar interactions

We investigate the effect of anisotropy and weak dipolar interactions on the magnetization of an assembly of nanoparticles with distributed magnetic moments, i.e., assembly of magnetic nanoparticles in the one-spin approximation, with textured or random anisotropy. The magnetization of a free particle is obtained either by a numerical calculation of the partition function or analytically in the low and high field regimes, using perturbation theory and the steepest-descent approximation, respectively. The magnetization of an interacting assembly is computed analytically in the range of low and high field, and numerically using the Monte Carlo technique. Approximate analytical expressions for the assembly magnetization are provided which take account of the dipolar interactions, temperature, magnetic field, and anisotropy. The effect of anisotropy and dipolar interactions are discussed and the deviations from the Langevin law they entail are investigated, and illustrated for realistic assemblies with the lognormal moment distribution.     

Non-Arrhenius relaxation of the Heisenberg model with dipolar and anisotropic interactions

The dynamical properties of a 2D Heisenberg model with dipolar interactions and perpendicular anisotropy are studied using Monte Carlo simulations in two different ordered regions of the equilibrium phase diagram. We find a temperature defining a dynamical transition below which the relaxation suddenly slows down and the system apart from the typical Arrhenius relaxation to a Vogel-Fulcher-Tamann law. This anomalous behavior is observed in the scaling of the magnetic relaxation and may eventually lead to a freezing of the system. Through the analysis of the domain structures we explain this behavior in terms of the domains dynamics. Moreover, we calculate the energy barriers distribution obtained from the data of the magnetic viscosity. Its shape supports our comprehension of both, the Vogel-Fulcher-Tamann dynamical slowing down and the freezing mechanism.