A systematic Monte Carlo simulation and renormalized perturbation theoretical study of the dielectric constant of the polarizable Stockmayer fluid

A systematic Monte Carlo (MC) simulation and perturbation theory (PT) study is reported for the dielectric constant of the polarizable Stockmayer fluid. Our MC simulations apply the ‘pair approximation for polarization interaction’ procedure suggested by P?edota et al. The theoretical approach is based on our newly introduced equation (Valiskó et al., 2002, Molec. Phys., 100, 559) which is a density expansion for the dielectric constant using Wertheim's renormalized PT method. The agreement between our MC and PT results is excellent for low to moderate dipole moments and polarizabilities. At stronger dipolar interactions ergodicity problems and anisotropic behaviour appear where simulation results become uncertain and the theoretical approach becomes invalid.     

Theory of polar fluids. I

We examine a classical fluid composed of molecules which contain a polarizable electric dipole with finite permanent moment. The long-ranged dipolar and the short-ranged interactions are treated on a different footing by expanding relative to a reference system characterized by the absence of electrostatic interactions. Extensions of graph theoretical techniques developed in an earlier paper are used to analyse the pair distribution function and the dielectric constant. Reduction of the number of graphs and their complexity is effected by introducing renormalizations of the permanent moment and the polarizability. The analysis leads to the definition of a new function w(12), which is free of terms dependent on the shape of the sample. For polar, polarizable molecules the direct correlation function lacks translational invariance; its role as a basic quantity is ceded to w(12). The pair distribution function and the dielectric constant ε are expressed in terms of w(12) and two closely related functions. Attention is drawn to an unsolved problem in dielectric theory, and an alternative formula for ε is presented in the form of a conjecture. An approximation for ε is formulated for the case in which the short-ranged non-dipolar interactions are independent of the molecular orientations. A simplified version is solved analytically.     

Effect of short and long range forces on the structure of water. II. Orientational ordering and the dielectric constant

The effects of short and long range interactions on the structure of water, both spatial and orientational, has been studied in detail by computing the full pair correlation function, site-site correlation functions, 2-dimensional site-site correlation functions in the (r _OO, r _OH) and (r _OO, r _HH) planes, dipole-dipole correlation function, radial Kirkwood g factor, and the dielectric constant. Two model potentials, the T1P4P and ST2, and their short range versions have been considered at ambient and elevated temperatures and under supercritical conditions. The Ewald summation under different conditions has been used to investigate also their effect on results. An analysis of the results shows that although all site-site correlation functions for the short and long range systems are similar, the orientational ordering in systems of different range may be considerably different, this evidence being provided mainly by the dipole-dipole correlation function and the radial Kirkwood factor. The orientational ordering is only short range in long range systems, whereas in short range systems the hydrogen bonding gives rise to a damped long range regular pattern of alignment. Nonetheless, the resulting dielectric constants for the short and long range systems coincide within the combined error bars. All findings are more pronounced at low temperatures but otherwise they are only marginally temperature and density dependent.     

Dielectric constant of polarizable,nonpolar fluids and suspensions

We study the dielectric constant of a polarizable, nonpolar fluid or suspension of spherical particles by use of a renormalized cluster expansion. The particles may have induced multipole moments of any order. We show that the Clausius-Mossotti formula results from a virtual overlap contribution. The corrections to the Clausius-Mossotti formula are expressed with the aid of a cluster expansion. The integrands of the cluster integrals are expressed in terms of two-body nodal connectors which incorporate all reflections between a pair of particles. We study the two- and three-body cluster integrals in some detail and show how these are related to the dielectric virial expansion and to the first term of the Kirkwood-Yvon expansion.     

A derivation of the compressibility equation for liquid metals

The Kirkwood and Buff compressibility equation for multicomponent systems is applied to an assembly of ions and electrons, where the Coulomb potential is replaced by the Yukawa potential. It is then shown that the resulting formula gives the Watabe-Hasegawa-Chihara compressibility equation in the limit of infinitesimal damping constant of the Yukawa potential.     

Three-body problem in the theory of the dielectric constant

We study the corrections to the Clausius-Mossotti formula for the dielectric constant of a disordered system of polarizable spherical particles. Previously we have derived an exact cluster expansion for the correction terms. Here we study the three-body correction in detail. We derive an explicit expression for the integrand of the three-body cluster integral for a system of polarizable point dipoles.     

Perturbation theory of scattering from irregular bodies

A perturbation solution is derived for the following problem: A time harmonic wave of amplitude ψ, propagating in a medium with wave number k, is incident on an irregular volume V, inside of which the propagation constant k′(r) can be an arbitrary function of | r |, where r is a position vector with origin inside V. The boundary conditions are that both ψ and its normal derivative ∂ψ/∂n may be discontinuous across the surface of V. Special cases of these conditions correspond to acoustic scattering, to B-wave scattering from a dielectric cylinder, or to the classical Dirichlet (ψ = 0) or Neumann (∂ψ/∂n = 0) surface conditions. An integral equation is derived that satisfies the appropriate differential equations both outside and inside the body, and satisfies the boundary conditions as well. This equation is reduced to a set of linear algebraic equations by expansion in a certain basis set and these linear equations are then solved in a perturbation approximation for the case that the surface of the body differs from a sphere or cylinder by a small parameter λ. Comparison is made with formulae in the literature, and except for some minor discrepancies, which are here corrected, there is general agreement.     

Electric field of an isolated charged impurity in an ionic crystal

The character of the behavior of the electric field created by a charged impurity in an ionic crystal is studied on the basis of both cluster and analytical approaches. In the cluster approach about 30 000 ions surrounding the impurity are taken into account. These ions are described in a model of polarizable sites. A direct calculation shows that the asymptote of the electric field of a charged impurity at lattice points can differ strongly from the one given by the Coulomb equation written for a homogeneous polarizable medium. The behavior of the electric field at intermediate distances, where the asymptotic behavior cannot yet be used, is studied in detail. It is found that the electric field is increased significantly in comparison to the Coulomb field in the region near the defect. The size of this (strongly polarized) region increases as the dielectric constant increases. These data are in qualitative agreement with the results obtained by Vikhnin et al. and account for the results of recent experiments designed to investigate polarization in reduced virtual ferroelectrics. Fiz. Tverd. Tela (St. Petersburg) 40, 662–667 (April 1998)     

Colour dielectric model of the proton

A model of the proton with its constituent quarks bound in a colour polarizable medium with dielectric constant varying as (a/r−b ²) from a fixed centre, is presented. The Dirac equation modified by the colour polarization is solved and the analytic expression for the wavefunction of the quarks obtained shows that quarks with higher energy lie closer to the fixed centre. The energy spectrum is equispaced without any continuum. A semiclassical approximation scheme yields closed orbits for quarks which have smaller size for higher energies and no orbits with size bigger than a certain maximum, thereby rendering the quarks permanently confined. The wavefunctions of the three quarks constituting the proton are used to calculate physical parameters of the proton such as its mass, charge radius and weak coupling constant which with suitable choice of the constantsa andb appearing in the dielectric constant agree fairly well with experimental results.     

Two-particle cluster integral in the expansion of the dielectric constant

We study in detail the two-particle cluster integral in the cluster expansion for the effective dielectric constant of a suspension of spherically symmetric polarizable inclusions embedded in a uniform medium. Although our form for the integrand differs from that derived earlier by Finkel'berg and by Jeffrey, we show that the integral is equivalent. The two-body dielectric problem for particles with an arbitrary radial dependence of the dielectric constant is solved by an expansion in spherical harmonics. Numerical results for some special models illustrate the importance of multipole contributions to the effective dielectric constant.     

From the N-body Schrödinger Equation to the Quantum Boltzmann Equation: a Term-by-Term Convergence Result in the Weak Coupling Regime

In this paper we analyze the asymptotic dynamics of a system of N quantum particles, in a weak coupling regime. Particles are assumed statistically independent at the initial time. Our approach follows the strategy introduced by the authors in a previous work [BCEP1]: we compute the time evolution of the Wigner transform of the one-particle reduced density matrix; it is represented by means of a perturbation series, whose expansion is obtained upon iterating the Duhamel formula; this approach allows us to follow the arguments developed by Lanford [L] for classical interacting particles evolving in a low density regime. We prove, under suitable assumptions on the interaction potential, that the complete perturbation series converges term-by-term, for all times, towards the solution of a Boltzmann equation. The present paper completes the previous work [BCEP1]: it is proved there that a subseries of the complete perturbation expansion converges uniformly, for short times, towards the solution to the nonlinear quantum Boltzmann equation. This previous result holds for (smooth) potentials having possibly non-zero mean value. The present text establishes that the terms neglected at once in [BCEP1], on a purely heuristic basis, indeed go term-by-term to zero along the weak coupling limit, at least for potentials having zero mean. Our analysis combines stationary phase arguments with considerations on the nature of the various Feynman graphs entering the expansion.     

The performance of non-polarizable and polarizable force-field parameter sets for ethylene glycol in molecular dynamics simulations of the pure liquid and its aqueous mixtures

Non-polarizable and polarizable force-field parameter sets for liquid ethylene glycol (EG) were developed for use in biomolecular simulation. In the polarizable models, electronic polarization effects were explicitly taken into account using the charge-on-spring method. The quality of the new force fields and two non-polarizable EG models taken from the literature was investigated by calculating relevant properties of the pure liquid and its aqueous mixtures, and comparing simulation results with experimental data. The performance of the EG models as a co-solvent in aqueous mixtures was additionally evaluated in a hydrophobic hydration study. The question was whether the experimentally known maximum in the solvation free enthalpy of argon at intermediate mixture compositions could be reproduced in the simulations. Values for the dielectric properties and excess free energy were found to be more off from experiment for the polarizable models than for the non-polarizable ones. However, a Kirkwood–Buff analysis of the aqueous mixtures and the hydrophobic hydration results exemplified that electronic polarization plays an important role in correctly describing attractive interactions between the EG and water co-solvent molecules. The trans/gauche ratio for ethylene glycol's O–C–C–O torsional angle was not found to systematically affect the properties of the pure liquid and aqueous mixtures.     

Fluids of polarizable hard spheres with dipoles and tetrahedral quadrupoles Integral equation results with application to liquid water

The mean spherical, linearized hypernetted chain and quadratic hypernetted chain approximations are solved for a fluid of hard spheres with embedded point dipoles and tetrahedral quadrupoles and this system is shown to be quite similar to the dipole-linear quadrupole case previously studied. However, tetrahedral quadrupoles have a larger influence upon the structural and thermodynamic properties and are slightly more effective in decreasing the dielectric constant from the purely dipolar value. Also we describe a simple self-consistent mean field theory which allows molecular polarizability to be taken into account. This approximation together with the integral equation methods is applied to a polarizable dipole-tetrahedral quadrupole fluid with water-like parameters. The dielectric constant of this system is found to be in good agreement with the experimental results for liquid water for temperatures ranging from 25°C to 300°C. The influence of molecular polarizability is shown to be very large. At 25°C the mean dipole moment is ～2·56 D compared with ～1·85 D in the gas phase and the dielectric constant increases from ～25 for non-polarizable particles to ～80 for the polarizable model.     

带强迫项变系数组合KdV方程的无穷序列复合型类孤子新解

为了获得变系数非线性发展方程的无穷序列复合型新解,研究了G′(ξ)G(ξ)展开法.通过引入一种函数变换,把常系数二阶齐次线性常微分方程的求解问题转化为一元二次方程和Riccati方程的求解问题.在此基础上,利用Riccati方程解的非线性叠加公式,获得了常系数二阶齐次线性常微分方程的无穷序列复合型新解.借助这些复合型新解与符号计算系统Mathematica,构造了带强迫项变系数组合KdV方程的无穷序列复合型类孤子新精确解.     

Quasilinearization method: Nonperturbative approach to physical problems

The general properties of the quasilinearization method (QLM), particularly its fast quadratic convergence, monotonicity, and numerical stability, are analyzed and illustrated on different physical problems. The method approaches the solution of a nonlinear differential equation by approximating the nonlinear terms by a sequence of linear ones and is not based on the existence of a small parameter. It is shown that QLM gives excellent results when applied to different nonlinear differential equations in physics, such as Blasius, Lane-Emden, and Thomas-Fermi equations, as well as in computation of ground and excited bound-state energies and wave functions in quantum mechanics (where it can be applied by casting the Schrödinger equation in the nonlinear Riccati form) for a variety of potentials most of which are not treatable with the help of perturbation theory. The convergence of the QLM expansion of both energies and wave functions for all states is very fast and the first few iterations already yield extremely precise results. The QLM approximations, unlike the asymptotic series in perturbation theory and 1/N expansions, are not divergent at higher orders. The method sums many orders of perturbation theory as well as of the WKB expansion. It provides final and accurate answers for large and infinite values of the coupling constants and is able to handle even supersingular potentials for which each term of the perturbation series is infinite and the perturbation expansion does not exist.     

Epsilon expansion for multicritical fixed points and exact renormalisation group equations

The Polchinski version of the exact renormalisation group equations is applied to multicritical fixed points, which are present for dimensions between two and four, for scalar theories using both the local potential approximation and its extension, the derivative expansion. The results are compared with the epsilon expansion by showing that the nonlinear differential equations may be linearised at each multicritical point and the epsilon expansion treated as a perturbative expansion. The results for critical exponents are compared with corresponding epsilon expansion results from standard perturbation theory. The results provide a test for the validity of the local potential approximation and also the derivative expansion. An alternative truncation of the exact RG equation leads to equations which are similar to those found in the derivative expansion but which gives correct results for critical exponents to order ε and also for the field anomalous dimension to order ε². An exact marginal operator for the full RG equations is also constructed.     

构造非线性发展方程的无穷序列复合型类孤子新解

为了构造非线性发展方程的无穷序列复合型类孤子新解, 进一步研究了G'(ξ)/G(ξ) 展开法. 首先, 给出一种函数变换, 把常系数二阶齐次线性常微分方程的求解问题转化为一元二次方程和Riccati方程的求解问题. 然后, 利用Riccati方程解的非线性叠加公式, 获得了常系数二阶齐次线性常微分方程的无穷序列复合型新解. 在此基础上, 借助符号计算系统Mathematica, 构造了改进的(2+1)维色散水波系统和(2+1)维色散长波方程的无穷序列复合型类孤子新精确解. 关键词： G'(ξ)/G(ξ)展开法')" href="#">G'(ξ)/G(ξ)展开法 非线性叠加公式 非线性发展方程 复合型类孤子新解     

Electrostatics of the ferroelectric phases of BaTiO3

Extensive theoretical calculations are reported here on the electrostatics of the three ferroelectric phases of BaTiO₃ using the static polarizable point-ion model. For each structure the following quantities have been calculated: monopole and dipole fields at ionic sites, field gradients, spontaneous polarization, high frequency dielectric constant and the Coulomb energy terms. The parameters of the model have been fitted on the basis of the experimental information on the tetragonal structure and then treated as constants for all the studied structures. The use of the experimental positional parameters of the orthorhombic structure gives such exceptional behaviour for all the calculated quantities that a redetermination of the structural parameters for this phase is suggested. Numerical study of the changes in the Coulomb energy as a function of the macroscopic depolarization potential demonstrated that the most stable state is achieved with the value zero for the potential.     

Dielectric behaviour and hydrogen bond molecular interaction study of formamide-dipolar solvents binary mixtures

The dielectric constant of binary mixtures of formamide with some common dipolar aprotic and protic solvents has been investigated at sixteen molar concentrations over the entire mixing range at 30 °C. The solvents used for binary mixtures with formamide are water, dimethylsulphoxide, N,N-dimethylformamide, acetone, 1,4-dioxane, mono-, di- and trihydric alcohols, and homologous series of 2-alkoxyethanol, 2-(2-alkoxyethoxy)ethanol, and ethylene glycol oligomers. The concentration dependent plots of excess dielectric constant and Kirkwood correlation factor were used to explore the complexes formed between unlike molecules, the molar ratio of a stable adduct, dipolar ordering, hydrogen-bond molecular connectivities, and their strength in the binary mixtures. Results confirmed that the complexation strength of dipolar aprotic solvents with formamide strongly depends on the value of solvent dielectric constant. The dependence of the hydrogen-bond complexation on number of hydroxyl groups and molecular size of the homologous series of the solvents is recognized from the comparative excess dielectric constant values of the mixed solvents.     

Statistical Behaviour of Three Boson Field Modes with Trilinear Interaction

The time variation of the density matrix for a system of three interacting boson field modes is described in the Schrödinger picture with the help of the unitary time development operator in coherent state basis. The nonlinear c-number equation for this operator is solved using a perturbation expansion in powers of the coupling constant. The explicit time dependence is obtained for the matrix elements of the total density matrix and of the particular density matrices of the individual modes. Photon number distributions and second order correlations are calculated for several initial situations.