Simulation of phase equilibria and interfacial properties of binary mixtures on the liquid-vapour interface using lattice sums

Molecular dynamics simulations of Lennard-Jones binary mixtures were performed to obtain phase equilibria and thermodynamic properties for the liquid—vapour interface. The dispersion interactions were handled using the lattice sum method where the full interaction is obtained and there is no requirement for any long range correction to the properties. The application of the method using the Lorentz—Berthelot combining rule for unlike interactions is discussed. The coexisting densities, adsorption of molecules at the interface and surface tension are the main results of this work. Coexisting properties were compared with Gibbs ensemble Monte Carlo results and with those of the grand canonical Monte Carlo method combined with the histogram reweighting technique, and good agreement was found. The lattice sum method results were compared with those of the spherically truncated and shifted potential to analyse the truncation effect. The adsorption of molecules at the interface and surface tension increase with interaction.     

The Luttinger sum rule in the slave-particle theories

The usual mean field decoupling procedure applied to the slave-particle representations of the problems with strong local interaction produces a resonant band, but violates the Luttinger sum rule for the physical single-electron propagator. The number of occupied resonant states is small and equal to the deviation from the sum rule, shedding doubt on the overall results. It is therefore argued and illustrated on the example of the Emery model for the high-T _c superconductors that, through the consistent application of the mean field procedure to the Hamiltonian and the propagators, the sum rule is restored and the resonant band conserved. In addition to the resonant band, the electron spectrum contains large number of occupied states close to the bare site-energy of the site with strong repulsion. These results are also related here to the other similar decoupling problems, which also lead to the breakdown of the Luttinger sum rule.Received: 2 July 2003, Published online: 9 September 2003PACS: 71.10.Fd Lattice fermion models (Hubbard model, etc.) - 71.27.+a Strongly correlated electron systems; heavy fermions     

Construction of localized basis for dynamical mean field theory

Many-body Hamiltonians obtained from first principles generally include all possible non-local interactions. But in dynamical mean field theory the non-local interactions are ignored, and only the effects of the local interactions are taken into account. The truncation of the non-local interactions is a basis dependent approximation. We propose a criterion to construct an appropriate localized basis in which the truncation can be carried out. This involves finding a basis in which a functional given by the sum of the squares of the local interactions with appropriate weight factors is maximized under unitary transformations of basis. We argue that such a localized basis is suitable for the application of dynamical mean field theory for calculating material properties from first principles. We propose an algorithm which can be used for constructing the localized basis. We test our criterion on a toy model and find it satisfactory.     

RPA correlation effects in radiative pion capture

A sum rule approach to radiative pion capture is given in terms of the energy-weighted and inverse-energy weighted sum rules. They are evaluated with RPA accuracy for Skyrme-like interactions. The static polarizabilities of the dipole, quadrupole and octupole isovector modes turn out to be the relevant quantities to determine the total branching ratios and mean photon energies.     

Sum rules for nuclear collective excitations

Characterizations of the response function and of integral properties of the strength function via a moment expansion are discussed. Sum rule expressions for the moments in the RPA are derived. The validity of these sum rules for both density independent and density dependent interactions is proved. For forces of the Skyrme type, analytic expressions for the plus three energy weighted sum rules are given for isoscalar monopole and quadrupole operators. From these, a close relationship between the monopole and quadrupole energies is shown and their dependence on incompressibility and effective mass is studied. The inverse energy weighted sum rule is computed numerically for the monopole operator, and an upper bound for the width of the monopole resonance is given. Finally the reliability of moments given by the RPA with effective interactions is discussed using simple soluble models for the hamiltonian, and also by comparison with experimental data.     

Bound-state perturbation method via SVZ sum rules in quantum mechanics

The perturbation method for bound states within the framework of the Shifman-Vainshtein-Zakharov sum rule method is studied on simple systems (linear harmonic oscillator, hydrogen atom) in external electric fields. It is pointed out that for stronger fields reasonable results for the ground-state energy can only be achieved when sum rules are written for the correction to the Euclidean Green function caused by the external field. Moreover, if the system is bound by a singular (Coulomb) potential, one needs to sum higher perturbative corrections to the Green function and to find a realistic approximation of the continuum contribution to the sum rules. The results are of relevance e.g. for calculations of nucleon magnetic moments and toponium properties via SVZ sum rules in QCD.     

Local structure theory: Calculation on hexagonal arrays,and interaction of rule and lattice

Local structure theory calculations⁷ are applied to the study of cellular automata on the two-dimensional hexagonal lattice. A particular hexagonal lattice rule denoted (3422) is considered in detail. This rule has many features in common with Conway'sLife. The local structure theory captures many of the statistical properties of this rule; this supports hypotheses raised by a study ofLife itself⁽⁶⁾. As inLife, the state of a cell under (3422) depends only on the state of the cell itself and the sum of states in its neighborhood at the previous time step. This property implies that evolution rules which operate in the same way can be studied on different lattices. The differences between the behavior of these rules on different lattices are dramatic. The mean field theory cannot reflect these differences. However, a generalization of the mean field theory, the local structure theory, does account for the rule-lattice interaction.     

Integral equation theory for fluids ordered by an external field: separable interactions

The structural and thermodynamical properties of classical fluids orientationally ordered by an external field are investigated by means of integral equation theories. A general theoretical framework for handling these theories is developed and detailed for the particular case of separable interactions between fluid particles. This approach is then illustrated for the case of two (off lattice) models: the ferromagnetic Heisenberg model and a simple liquid crystal model, for which the numerical solution of integral equations such as the Percus-Yevick, the hypernetted chain, and the reference hypernetted chain closure equations are presented and compared with Monte Carlo simulation results and the analytical solution of the mean spherical approximation. The zero-field case is also examined, and the spontaneous ordering is analyzed in detail, mainly in what concerns the appearance of infinite wavelength singularity in the Ornstein-Zernike equation and the relation with the one-body closure equations and the long range orientational ordering that occurs. In particular, it is shown that the Wertheim one-body closure equation appears as a sum rule compatible with the Ornstein-Zernike equation. The relation between the elastic constant and the long range tail of the pair correlation function is made explicit. In particular, the long range behavior of the various terms in the expansion of the pair correlation function is depicted. The numerical investigation of the two models shows that it is not possible to discriminate between the four integral equations, as to which one would be the most accurate in all cases. The general trends in the thermodynamical and structural properties seem to indicate that the Percus-Yevick approximation is generally better in the strong ordering case, whereas the reference hypernetted chain approximation might be better suited to the study of the isotropic phase and the low ordering regimes.     

Do we understand the role of incoherent interactions in many-body physics?

Recent developments in many-body quantum chaos show that a quantum system with strong incoherent interactions can still be described with the aid of mean quasiparticle occupation numbers as in Fermi liquid theory. We use these ideas and the geometric chaoticity of angular momentum coupling to explain the predominance of ground states with zero spin and the maximum possible spin for a system of randomly interacting fermions in a rotationally invariant mean field (an analog of the Hund rule). We show that spin ordering coexists with the chaotic features of the ground-state wave functions.     

Meson fields, exchange currents and progenitor sum rules

The theory of the integrated photoabsorption cross section and the dipole sum rule is reviewed. A new progenitor sum rule, in which meson fields appear explicitly, is derived from a field theory of interacting pions and nucleons. The relation of this sum rule to previous results obtained in a potential theory is elucidated, and the role of neutron-proton correlations in nuclear ground states is discussed in terms of their effect on the dipole sum rule. The inclusion of ρ-mesons (again in an oversimplified theory) and their contribution to progenitor sum rules is also mentioned.     

On the collective modes of infinite nuclear matter

In this paper we study the longitudinal collective vibrations of infinite nuclear matter in the long wavelength limit. We present an alternative method for solving the Landau equations which allows analytical expressions for the response function, the odd sum rules and the strength of the modes. We solve the theory for a selection of Skyrme interactions and we also consider the properties of the ground state of the system specifically associated with the four collective states which exist in nuclear matter. The relationship between the quantum mechanical response function and the corresponding classical hydrodynamical quantity is explored and the approximate results obtained through sum rules are compared with the exact solutions of the RPA equations. Finally the Landau parameters obtained with the Skyrme forces are tested against the antisymmetry property of the forward particle-hole scattering amplitude on the Fermi surface and the enhancement factor in the photonuclear dipole sum rule.     

Spin-dependent sum rule for high-energy neutrino reactions

We present a sum rule which related the inclusive cross section for high-energy neutrino scattering on polarized proton targets to the axial-vector coupling constant. The derivation of the sum rule rests on the equal-time algebra of the time-components of the weak currents. The sum rule also provides a discriminatory test of unified models of weak and electromagnetic interactions based on spontaneously-broken gauge symmetry.     

Toward finite quantum field theories

The properties that make theN=4 super Yang-Mills theory free from ultraviolet divergences are (i) a universal coupling for gauge and matter interactions, (ii) anomaly-free representations, (iii) no charge renormalization, and (iv) if masses are explicitly introduced into the theory, then these are required to satisfy the mass-squared supertrace sum rule _s=0,1/2(–1)^2s+1(2s+1)M _s ² =0. FiniteN=2 theories are found to satisfy the above criteria. The missing member in this class of field theories are finite field theories consisting ofN=1 superfields. These theories are discussed in the light of the above finiteness properties. In particular, the representations of all simple classical groups satisfying the anomaly-free and no-charge renormalization conditions for finiteN=1 field theories are discussed. A consequence of these restrictions on the allowed representations is that anN=1 finiteSU (5)-based model of strong and electroweak interactions can contain at most five conventional families of quarks and leptons, a constraint almost compatible with the one deduced from cosmological arguments.     

Collective modes,damping, and the scattering function in classical liquids

An exact representation for the density-density response function is presented. This representation is a generalization of the result obtained in the mean field approximation and amounts to replacing the static, effective potential by one which is both wavenumber- and frequency-dependent. This potential possesses both a real and an imaginary part; the latter describes the collisional damping of collective modes. Analyticity and sum rule arguments are used to describe the basic properties of this complex potential. The formalism allows us to write an exact formula for the scattering functionS(k, ) in which the basic unknown is the collisional damping function. Using a small portion of the recent experimental data on coherent neutron scattering in liquid argon, we are able to calculateS(k, ) and other quantities of interest and to make comparisons with the rest of the data.     

Liquid–vapour equilibrium of n -alkanes using interface simulations

Molecular Dynamics simulations were performed to calculate liquid–vapour coexisting properties of n-alkane chains up to 16 carbon atoms using interface simulations. The lattice sum or Ewald method on the dispersion forces of the Lennard–Jones potential was applied to calculate the full interaction. The liquid and vapour coexisting densities were obtained for two flexible force field models, NERD and TraPPE-UA, where the intermolecular interactions are of the Lennard–Jones type. We have recently shown [P. Orea, J. López-Lemus, and J. Alejandre, J. Chem. Phys. 123, 114702 (2005)] that the liquid–vapour densities for simple fluids do not depend on interfacial area and therefore it is possible to use a small number of molecules in a simulation. We show that the same trend is found on the simulation of these hydrocarbon molecules. The phase diagram of ethane/n-decane binary mixtures is also obtained at 410.95 K for the NERD model. The simulation results from this work were compared with those obtained using methods with interfaces using large cut-off distances and with methods without interfaces for the same potential model. In both comparisons, excellent agreement was found. The results of liquid density from the TraPPE-UA model are in good agreement with experimental data while those from the NERD model are underestimated at low temperatures. Our findings are consistent with results published by other authors for small hydrocarbons.     

The nuclear Coulomb sum rule in a relativistic model

The nuclear Coulomb sum rule is investigated in a relativistic quantum field theory of the nucleus based on baryons and mesons. First an effective, local, covariant, conserved electromagnetic current operator is constructed for the many-baryon system. It describes the electromagnetic structure of an isolated nucleon; the lowest-mass two-pion contribution to the spectral weight functions of the form factors is contained in it. The sum rule is then evaluated in a model based on baryons and neutral scalar and vector mesons. In the mean-field approximation (MFT) this model correctly describes the saturation properties of nuclear matter. The “one-body” term in the sum rule can be evaluated exactly through the use of the canonical anticommutation relations for the baryon field and the identification of conserved quantities. The remaining relativistic two-body contribution is evaluated in the MFT. Meson contributions to the sum rule at large momentum transfers $\text{q}\text{2k}{}_{\mathrm{<mtext>F</mtext>}}\text{? 1}$ completely dominate anticipated static, short-range, two-nucleon correlation contributions to the non-relativistic Coulomb sum rule. One possible implication is that the nucleus must (at least) be considered as a dynamic system of mesons and baryons.     

Liquid–vapour transition of the long range Yukawa fluid

Two liquid state theories, the self-consistent Ornstein–Zernike equation (SCOZA) and the hierarchical reference theory (HRT) are shown, by comparison with Monte Carlo simulations, to perform extremely well in predicting the liquid–vapour coexistence of the hard-core Yukawa (HCY) fluid when the interaction is long range. The long range of the potential is treated in the simulations using both an Ewald sum and hyperspherical boundary conditions. In addition, we present an analytical optimized mean field theory which is exact in the limit of an infinitely long-range interaction. The work extends a previous one by C. Caccamo, G. Pellicane, D. Costa, D. Pini, and G. Stell, Phys. Rev. E 60, 5533 (1999) for short-range interactions.     

Multiphoton free-free transitions in a spatially inhomogeneous laser field

Summary The results of an investigation are presented in which it is shown how the spatial inhomogeneity of a laser field modifies the multiphoton free-free transition cross-sections compared to the case of a homogeneous field. This kind of investigation is required to make more close contact with experiments in intense fields, as in these cases the inhomogeneity is produced by the focusing of the laser beam. Furthermore, taking into account the intensity spatial distribution allows us to achieve in an effective way the asymptotic decoupling of the scattered particles from the field, which is very important for theoretical models using asymptotic initial and final states embedded in the field. Differential and total cross-sections are calculated over a wide range of parameters as functions of the scattering angle, of the incoming-particle energy and of the laser intensity and frequency. The laser spatial inhomogeneity is found to wash out most of the oscillating behaviour of multiphoton differential cross-sections, derived within the model of a homogeneous laser. Little modifications are, instead, found in the total cross-sections which are simply scaled to slightly lower values. Crosssections with zero photon exchange are increased, while those with photon exchanges are lowered. This yields the result that the sum of all the ≪inhomogeneous≫ cross-sections is equal to the sum of all the ≪homogeneous≫ ones (sum rule). The multiphoton free-free transition differential cross-sections are found to be very sensitive quantities which may be used to get information on the laser properties and on their nonlinear behaviour, when these are not precisely known. To speed up publication, the authors of this paper have agreed to not receive the proofs for correction.     

Quasiparticle properties of strongly correlated electron systems with itinerant metamagnetic behavior

A brief account of the zero temperature magnetic response of a system of strongly correlated electrons in strong magnetic field is given in terms of its quasiparticle properties. The scenario is based on the paramagnetic phase of the half-filled Hubbard model, and the calculations are carried out with the dynamical mean field theory (DMFT) together with the numerical renormalization group (NRG). As well known, in a certain parameter regime one finds a magnetic susceptibility which increases with the field strength. Here, we analyze this metamagnetic response based on Fermi liquid parameters, which can be calculated within the DMFT-NRG procedure. The results indicate that the metamagnetic response can be driven by field-induced effective mass enhancement. However, also the contribution due to quasiparticle interactions can play a significant role. We put our results in context with experimental studies of itinerant metamagnetic materials.     

Force sum-rule and static electronic polarizability of atoms and microstructures

A sum rule is derived within density functional formalism for the response of an electronic system to a uniform electrostatic field. The sum rule states that the sum of the electrostatic forces on the positive charge background equals zero. The sum rule provides a useful test of electronic polarizability calculations for atoms and microstructures. It also leads to a self-consistency relationship for the induced charge density obtained in image-plane calculations.