Perturbation theory for non-axial molecular fluids

The thermodynamic perturbation theory in which all angle-dependent interactions are considered as a perturbation of the central potential is applied to study the equilibrium properties of a fluid composed of non-axial molecules. The influence of a large number of anisotropic pair and three-body non-additive interactions have been taken into account. Using the same set of force parameters the calculation is made for gaseous pressure second and third virial coefficients and liquid phase thermodynamic properties (Helmholtz free-energy, configurational energy, pressure and entropy). It is shown that the non-axial approximation is an improvement over the axial one. Excellent agreement between theory and experiment is obtained for ethylene.     

Perturbation theory for equilibrium properties of a binary mixture of hard discs

The radial distribution function (RDF) and thermodynamic properties of a two-dimensional hard-disc mixture are calculated by using the perturbation theory. Numerical results are given for theRDF, pressure and excess-free energy of the binary mixture of both additive and non-additive hard discs. It is found that the thermodynamic properties of the binary mixture of non-additive hard discs increase with Δ, the non-additive parameter.     

Perturbation theory for mixtures of discrete potential fluids

A thermodynamic perturbation theory for mixtures of fluids composed of particles interacting via discrete potentials is presented, based on previous work for pure component systems. Square-well and square-shoulder mixtures are accurately described by this theory, giving the necessary information for studying a wide range of discrete potential fluids. As an example of this, the theory is applied to a discrete Lennard-Jones mixture, obtaining very good results when compared against computer simulation values. The scope of this work is to implement perturbation theory for discrete potential systems in modern theories for complex fluids.     

Perturbation theory for fluids of rod-like molecules interacting via the Kihara potential

For systems of molecules interacting via the Kihara core potential a first-order perturbation theory is proposed. As a reference system soft convex bodies are employed with interactions given by the entire repulsive part of the original pair potential (i.e. for surface-to-surface distances smaller than that of the potential minimum). Their equilibrium behaviour is interpreted on the basis of the representative hard convex bodies-parallel convex bodies to the assumed cores with temperature-dependent thickness. The shape of the distribution function was approximated by the Verlet-Weis form. Theoretical expressions were used for the determination of the thermodynamic functions of the Kihara-molecule systems at several reduced temperatures and compared with experimental data for nitrogen.     

Perturbation theory based direct correlation function for fluids with hard core potentials

Using second-order Barker–Henderson perturbation theory we are able to derive an explicit expression for the direct correlation function of fluids with hard core potentials. Using the obtained direct correlation function, one can explicitly calculate all thermodynamic properties of simple fluids with hard core potentials. Comparisons with computer simulation data show good agreement for both thermodynamic properties and the static structure factor of the hard core double Yukawa potential.     

Density-functional theory for polymer fluids with molecular weight polydispersity

We develop a density-functional theory for polydisperse polymer fluids satisfying the Schulz-Flory distribution. The resulting equations are remarkably simple and quickly solved, the computational effort scaling with the polydispersity index, rather than the average molecular weight. Equilibrium, or "living", polymers enter naturally as very polydisperse samples. We illustrate the importance of polydispersity on colloid stability by investigating interactions between adsorbing and nonadsorbing surfaces. Significant free energy barriers are present in monodisperse samples, but these diminish as the degree of polydispersity increases.     

Perturbation theory for kinds

In this paper we prove the validity of formal asymptotic results on perturbation theory for kind solutions of the sine-Gordon equation, originally obtained by McLaughlin and Scott. We prove that for appropriate perturbations, of size in an appropriate norm, slowly varying in time in the rest frame of the kink, the shape of the kink is unaltered in theL norm toO() for a time ofO(1/). The kink parameters, which represent its velocity and centre, evolve slowly in time in the way predicted by the asymptotics. The method of proof uses an orthogonal decomposition of the solution into an oscillatory part and a one-dimensional zero-mode term. The slow evolution of the kink parameters is chosen so as to suppress secular evolution of the zero-mode.Partially supported as a graduate student at Princeton University of NSF grant 215 6211     

Perturbation theory for thermodynamic properties of a ν-dimensional square-well fluid

The Barker-Henderson perturbation theory is used for a ν-dimensional fluid with square-well potential. Analytic expressions are given for the equation of state, excess free energy per particle and internal energy. The numerical results are discussed. A significant feature is the increase of the thermodynamic properties with increasing dimensionality.     

Perturbation theory for velocity-dependent potentials

In the presence of a velocity-dependent Kisslinger potential, the partial-wave, time-independent Schr?dinger equation with real boundary conditions is written as an equation for the probability density. The changes in the bound-state energy eigenvalues due to the addition of small perturbations in the local as well as the Kisslinger potentials are determined up to second order in the perturbation. These changes are determined purely in terms of the unperturbed probability density, the perturbing local potential, as well as the Kisslinger perturbing potential and its gradient. The dependence on the gradient of the Kisslinger potential stresses the importance of a diffuse edge in nuclei. Two explicit examples are presented to examine the validity of the perturbation formulas. The first assumes each of the local and velocity-dependent parts of the potential to be a finite square well. In the second example, the velocity-dependent potential takes the form of a harmonic oscillator. In both cases the energy eigenvalues are determined exactly and then by using perturbation theory. The agreement between the exact energy eigenvalues and those obtained by perturbation theory is very satisfactory. Received: 24 May 2002 / Accepted: 15 July 2002 / Published online: 3 December 2002 RID="a" ID="a"e-mail: mij@hu.edu.jo Communicated by V. Vento     

Perturbation theory for bending potentials

An efficient perturbative method is developed to facilitate the treatment of the anharmonicity of bending degrees of freedom. The Rosen-Morse and sec² potentials are transformed so that perturbation theory may be applied easily. For a model problem it is found that the difference between the energy levels obtained from perturbation theory and the exact energy levels is less than 0·1 cm^-1 for the first six energy levels.     

Equivalence of integral equations in the molecular theory of fluids

It is proven that, under physically reasonable conditions, the correlation functions satisfying the BBGKY equations for an infinite system are also solutions of the Mayer-Montroll and Kirkwood-Salsburg equations. The relation between these correlation functions and the probability distributions for finding a fixed number of particles in a given finite region of an infinite system is investigated. The Gibbsian nature of these probability distributions is shown to depend on the range of the intermolecular forces.     

Density functional theory for molecular orientation of hard rod fluids in hard slits

A density functional theory (DFT) is used to investigate molecular orientation of hard rod fluids in a hard slit. The DFT approach combines a modified fundamental measure theory (MFMT) for excluded-volume effect with the first order thermodynamics perturbation theory for chain connectivity. In the DFT approach, the intra-molecular bonding orientation function is introduced. We consider the effects of molecular length (i.e. aspect ratio of rod) and packing fraction on the orientations of hard rod fluids and flexible chains. For the flexible chains, the chain length has no significant effect while the packing fraction shows slight effect on the molecular orientation distribution. In contrast, for the hard rod fluids, the chain length determines the molecular orientation distribution, while the packing fraction has no significant effect on the molecular orientation distribution. By making a comparison between molecular orientations of the flexible chain and the hard rod fluid, we find that the molecular stiffness distinctly affects the molecular orientation. In addition, partitioning coefficient indicates that the longer rodlike molecule is more difficult to enter the confined phase, especially at low bulk packing fractions.     

Equilibrium theory of molecular fluids: Structure and freezing transitions

In this article we review equilibrium theory of molecular fluids which includes structure and freezing transitions. The application of the theory to evaluate the pair correlation functions using Integral Equation methods and Computer Simulations have been discussed. Freezing of classical complex fluids based on the density functional approach is also discussed and compare a variety of its versions. Transitions discussed are sensitive to the value of direct correlation functions of the effective liquid which is required as an input information in the theory. Accurate evaluation of pair correlation functions is emphasized. Calculation of these correlation functions which pose problems in the case of ordered phases is discussed. The pair correlation functions of the ordered phase, which are supposed to be made up of two contributions, one that preserves the symmetry of the isotropic phase and a second that breaks it, are discussed. A new free-energy functional developed for an inhomogeneous system that contains both symmetry conserved and symmetry broken parts of the direct pair correlation function is discussed. The most useful three dimensional reference interaction site model (3D-RISM) and its extension done recently by many workers is discussed. Application of this theory to a large variety of complex systems in combination with the density functional theory method implemented in the Amsterdam density functional software package is discussed. Coupling of the 3D-RISM salvation theory with molecular dynamics in the Amber molecular dynamics package is also given.     

Perturbation theory for relativistic Lee model

Proof of convergence of perturbation series for the S matrix elements is given for the relativistic Lee model, subject to the validity of an hypothesis explained in the paper. A proof of isometry for the wave operators is also given.     

Perturbation theory for QED bound states

A new method is presented for deriving a systematic perturbative expansion for QED bound states, which does not rely upon solving any new or old equation. The starting point is a given nonperturbative zeroth order Green's function, obtained by a suitable “relativistic dressing” of the nonrelativistic Green's function for the Schrödinger equation with Coulomb potential, which embodies the Coulombic bound states and is known. The comparison with the complete Green's function as given by standard perturbative QED gives a perturbative kernel which is then used for the expansion of the QED Green's function in terms of the given non-perturbative zeroth order Green's function.     

Perturbation theory for a bound polaron

Perturbation theory is applied suitably to obtain an expression, valid for all types of binding, for the shift in ground state energy of an electron bound to a coulomb impurity in a polar semiconductor.