Yukawa potentials in systems with partial periodic boundary conditions. I. Ewald sums for quasi-two-dimensional systems

Yukawa potentials are often used as effective potentials for systems such as colloids, plasmas, etc. When the Debye screening length is large, the Yukawa potential tends to the non-screened Coulomb potential; in this small screening limit, or Coulomb limit, the potential is long-ranged. As is well known in computer simulation, a simple truncation of the long-ranged potential and the minimum image convention are insufficient to obtain accurate numerical data on systems. The Ewald method for bulk systems, i.e. with periodic boundary conditions in all three directions of space, has already been derived for the Yukawa potential [Molec. Phys. 88, 1357 (1996); J. Chem. Phys. 113, 10459 (2000)], but for systems with partial periodic boundary conditions, the Ewald sums have only recently been obtained [J. Chem. Phys. 126, 056101 (2007)]. In this paper, we provide a closed derivation of the Ewald sums for Yukawa potentials in systems with periodic boundary conditions in only two directions and for any value of the Debye length. Special attention is paid to the Coulomb limit and its relation to the electroneutrality of systems.     

Lekner summations and Ewald summations for quasi-two-dimensional systems

The purpose of this work is to carry out a comparison between the Ewald quasi-2D and Lekner summation methods. These methods were derived to treat the long-range electrostatic interactions in systems periodic in two directions, but bound in the third. The comparison is performed by Monte Carlo simulations on a very simple system, a bilayer of point ions; samplings of the phase space, average energies and structure functions are compared. When correctly implemented, the Lekner summation method is found to be in close agreement with the Ewald quasi-2D method; otherwise, a very complicated bias may plague computations.     

Molecular dynamics simulations of liquid water using various long-range electrostatics techniques

Water is one of the most extensively studied molecules, owing to its crucial role in biological processes. The water molecule is both highly polar and highly polarizable. Properties of water computed from molecular simulations are therefore critically dependent on both the intermolecular potential and the method for computing long-range electrostatic corrections. In this paper, the effects of the potential and the long-range electrostatic corrections are quantified for liquid water from 260 to 400?K. Simulations were carried out for a system of 256 molecules in the NVT ensemble. Thermodynamic, structural, dynamical, hydrogen bonding and dielectric properties have been computed for the flexible SPC and rigid SPC, SPC/E, TIP4P, TIP4P-Ew and TIP4P-FQ potentials, using the Lekner, Ewald and reaction field techniques to handle long-range electrostatics. The Lekner method gave the best overall agreement with experimental data, while the reaction field approach produced poorer results. Some measurable differences were found between the Lekner and Ewald techniques. For dielectric properties, the performance of the TIP4P-FQ model was superior relative to other potentials. For 256 molecules, the computational speeds of the Ewald and reaction field methods were found to be 2.5 to 3 times and 3.5 to 5 times faster than the Lekner technique, respectively.     

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.     

Monte Carlo simulations of primitive models for ionic systems using the Wolf method

Thermodynamic and structural properties of primitive models for electrolyte solutions and molten salts were studied using NVT and NPT Monte Carlo simulations. The Coulombic interactions were simulated using the Wolf method [D. Wolf, Phys. Rev. Lett. 68, 3315 (1992); D. Wolf, P. Keblinnski, S. R. Phillpot, and J. Eggebrecht, J. Chem. Phys. 110, 8254 (1999)]. Results for 1?:?1 and 2?:?1 charge ratio electroneutral systems are presented, using the restricted and non-restricted primitive models, as well as a soft PM pair potential for a monovalent salt [J.-P. Hansen and I. R. McDonald, Phys. Rev. A 11, 2111 (1975)] that has also been used to model 2?:?12 and 1?:?20 asymmetric colloidal systems, with size ratios 1?:?10 and 2?:?15, respectively [B. Hribar, Y. V. Kalyuzhnyi, and V. Vlachy, Molec. Phys. 87, 1317 (1996)]. We present the predictions obtained for these systems using the Wolf method. Our results are in very good agreement with simulation data obtained with the Ewald sum method as well as with integral-equation theories results. We discuss the relevance of the Wolf method in the context of variable-ranged potentials in molecular thermodynamic theories for complex fluids.     

Ewald method for polytropic potentials in arbitrary dimensionality

The Ewald summation technique is generalized to power-law 1/| r | ^k potentials in three-, two- and one-dimensional geometries with explicit formulae for all the components of the sums. The cases of short-range, long-range and ‘marginal’ interactions are treated separately. The jellium model, as a particular case of a charge-neutral system, is discussed and the explicit forms of the Ewald sums for such a system are presented. A generalized form of the Ewald sums for a non-cubic (non-square) simulation cell for three- (two-) dimensional geometry is obtained and its possible field of application is discussed. A procedure for the optimization of the involved parameters in actual simulations is developed and an example of its application is presented.     

Transport coefficients of the Yukawa one-component plasma

We present equilibrium molecular-dynamics computations of the thermal conductivity and the two viscosities of the Yukawa one-component plasma. The simulations were performed within periodic boundary conditions, and Ewald sums were implemented for the potentials, the forces, and for all the currents which enter the Kubo formulas. For large values of the screening parameter, our estimates of the shear viscosity and the thermal conductivity are in good agreement with the predictions of the Chapman-Enskog theory.     

Effect of electrostatics techniques on the estimation of thermal conductivity via equilibrium molecular dynamics simulation: application to methane hydrate

Equilibrium molecular dynamics (MD) simulations for three system sizes of fully occupied methane hydrate have been performed at around 265 K to estimate the thermal conductivity using the Ewald, Lekner, reaction field, shifted-force and undamped Fennell–Gezelter methods. The TIP4P water model was used in conjunction with a fully atomistic methane potential with which it had been parameterized from quantum simulation. The thermal conductivity was evaluated by integration of the heat flux autocorrelation function (ACF) derived from the Green–Kubo formalism; this approach vas validated by estimation of the average phonon mean free path. The thermal conductivities predicted by non-periodic techniques were in reasonable agreement with the experimental results of 0.62 and 0.68 W/m K, although it was found that the estimates by the non-periodic techniques were up to 25% larger than those of Lekner and Ewald estimates, particularly for larger systems. The results for the Lekner method exhibited the least variation with respect to system size. A decomposition of the heat flux vector into its respective contributions revealed the importance of electrostatic interactions, and how different electrostatic treatments affect the contribution to the thermal conductivity.     

Electrostatic interactions in molecular dynamics simulation of a three-dimensional system with periodicity in one direction

The Mellin transform and Poisson summation formula are used to derive an expression for the Coulomb interaction energy of a three-dimensional system with periodicity in one direction. Initially, calculations are performed for interactions characterized by any inverse power and, using the analytical continuation of the energy function, one obtains the final expression for the interaction energy of charges. We consider also a special case when two different charges are located on a line parallel to the periodicity direction. The energy and force expressions are identical to those obtained from the Lekner summation which is simply a sum over reciprocal lattice terms. The convergence behaviour of the Lekner summation is compared with that based on the Ewald type approach.     

Exact matrix elements for general two-body central-force interactions,expressed as sums of products

ABSTRACT

In a manner similar to but distinct from concurrent tensor efforts in electronic structure, it is shown that the Laplace transform can serve as a generator for a sum-of-products (SOP) form that allows one to write essentially any function of distance between two particles (i.e. any central force potential) as an exact two-body matrix. In particular, exact expressions for the Coulomb, Yukawa and long-range Ewald two-body operators are evaluated in a band-limited (Sinc function) basis. The resultant exact, full-basis, SOP representations for these interaction potentials – acting in conjunction with an external harmonic confining field – are validated via comparison with energy eigenstate solutions obtained via an independent calculation based on separation of variables. The new two-body matrix representations may have substantial impact in any of the many disciplines in which pair-wise central force interactions are relevant – especially, electronic structure and dynamics.     

An Elementary Proof of Lyapunov Exponent Pairing for Hard-Sphere Systems at Constant Kinetic Energy

The conjugate pairing of Lyapunov exponents for a field-driven system with smooth inter-particle interaction at constant total kinetic energy was first proved by Dettmann and Morriss [Phys. Rev. E 53:R5545 (1996)] using simple methods of geometry. Their proof was extended to systems interacting via hard-core inter-particle potentials by Wojtkowski and Liverani [Comm. Math. Phys. 194:47 (1998)], using more sophisticated methods. Another, and somewhat more direct version of the proof for hard-sphere systems has been provided by Ruelle [J. Stat. Phys. 95:393 (1999)]. However, these approaches for hard-sphere systems are somewhat difficult to follow. In this paper, a proof of the pairing of Lyapunov exponents for hard-sphere systems at constant kinetic energy is presented, based on a very simple explicit geometric construction, similar to that of Ruelle. Generalizations of this construction to higher dimensions and arbitrary shapes of scatterers or particles are trivial. This construction also works for hard-sphere systems in an external field with a Nosé–Hoover thermostat. However, there are situations of physical interest, where these proofs of conjugate pairing rule for systems interacting via hard-core inter-particle potentials break down.     

Lekner summation of dipolar interaction in quasi-two-dimensional simulations

The Lekner method for calculation of electrostatic interactions in periodically replicated simulation cells is extended to quasi-two-dimensional systems of particles with dipolar interactions. The electric field, potential energy, forces and torques are expressed through rapidly converging series of modified Bessel functions. The method contains no arbitrary parameters, and has no limitations on the simulation box width.     

Entangled quantum heat engines based on two two-spin systems with Dzyaloshinski-Moriya anisotropic antisymmetric interaction

We construct an entangled quantum heat engine (EQHE) based on two two-spin systems with Dzyaloshinski-Moriya (DM) anisotropic antisymmetric interaction. By applying the explanations of heat transferred and work performed at the quantum level in Kieu’s work [Phys. Rev. Lett. 93, 140403 (2004)], the basic thermodynamic quantities, i.e., heat transferred, net work done in a cycle and efficiency of EQHE are investigated in terms of DM interaction and concurrence. The validity of the second law of thermodynamics is confirmed in the entangled system. It is found that there is a same efficiency for both antiferromagnetic and ferromagnetic cases, and the efficiency can be controlled in two manners: (1) only by spin-spin interaction J and DM interaction D; (2) only by the temperature T and concurrence C. In order to obtain a positive net work, we need not entangle all qubits in two two-spin systems and we only require the entanglement between qubits in a two-spin system not be zero. As the ratio of entanglement between qubits in two two-spin systems increases, the efficiency will approach infinitely the classical Carnot one. An interesting phenomenon is an abrupt transition of the efficiency when the entanglements between qubits in two two-spin systems are equal.     

Existence and vanishing of the breathing mode in strongly correlated finite systems

One of the fundamental eigenmodes of finite interacting systems is the mode of uniform radial expansion and contraction-the breathing mode (BM). Here we show in a general way that this mode exists only under special conditions: (i) for harmonically trapped systems with interaction potentials of the form 1/rgamma (gamma in R not equal 0) or log(r), or (ii) for some systems with special symmetry such as single-shell systems forming platonic bodies. Deviations from the BM are demonstrated for two examples: clusters interacting with a Lennard-Jones potential and parabolically trapped systems with Yukawa repulsion. We also show that vanishing of the BM leads to the occurrence of multiple monopole oscillations which is of importance for experiments.     

Long-Ranged Correlations in Bounded Nonequilibrium Fluids

In a recent paper, Liu and Oppenheim [J. Stat. Phys. 86:179 (1997)] solve the fluctuating heat diffusion equation for a bounded system with a temperature gradient. This note demonstrates that, contrary to their claims, their solution for the temperature correlation function is indeed long-ranged and reduces to that of Garcia et al.[J. Stat. Phys. 47:209 (1987)].     

Empirical bridge function for strongly coupled yukawa systems

A simple bridge function for strongly coupled Yukawa systems is developed based upon a form previously extracted for a one-component plasma [H. Iyetomi, S. Ogata, and S. Ichimaru, Phys. Rev. A 46, 1051 (1992)]. Using the proposed bridge function in the modified hypernetted chain theory, excellent agreement is obtained with molecular dynamics simulations and the compressibility sum rule is satisfied to within a few percent. This result offers a simple and very accurate method to quickly compute correlation functions for Yukawa systems.     

Analysis of mass transfer in dissipative nonideal systems: Numerical simulation

The results of a numerical analysis of mass transfer in extended quasi-two-dimensional and three-dimensional dissipative nonideal systems are presented. Pair interaction between particles is modeled by isotropic repulsive potentials represented by combinations of power laws and exponentials. Simulations are performed for parameter values characteristic of laboratory dusty plasmas. It is shown that short-time particle dynamics in nonideal liquid systems is similar to evolution of thermal oscillations at crystal lattice sites.     

Variational Bound States of Screened Potentials

Anumber of years ago, a calculational scheme was introduced by Stubbins [Phys. Rev. A48, 220 (1993)] to compute the energies of both the Hulthén and Yukawa potentials. The method introduces a particular ansatz for solving the Schrödinger equation with screened Coulomb type potentials. In this work, we wish to review the method of Stubbins and to show that it is, in fact, equivalent and a subset of a more systematic (and hence more useful) variational scheme [Zhou et al. Phys. Rev. A51, 3337 (1995)]. This variational approach involves the construction of a basis by taking derivatives of the variational parameters of the system. The eigenvalues of the Hamiltonian matrix are then minimized with respect to these parameters yielding a “best guess” upper bound on the energies.     

Multiple series of shape resonances and near-zero-energy cross section enhancements in photoionization of hydrogen-like ions with screened coulomb interaction

The recently discovered multiple series of shape resonances and near-zero-energy enhancements in photoionization cross section of hydrogen-like atomic systems with screened Coulomb (Yukawa type) interaction [Phys. Rev. A 80, 063404 (2009)] are studied in detail, in particular their evolution with the variation of the screening strength of the potential. The conditions for appearance of these multiple series of cross section features are identified and related to certain critical screening strengths of the potential. A relation between the appearance of Cooper minima and shape resonaces in the photoionizations cross section has been established. It is also shown that the s-channel of np photoionization for a fixed photoelectron energy exhibits Ramsauer-Townsend minima in the screening length variable.     

Coupling by charge transfer: role in bond stabilization for open-shell systems and ionic molecules and in harpooning and proton attachment processes

A variety of phenomena of apparently different nature can be compacted and described within a unifying picture by taking into account the role of the charge transfer interaction. Relevant information on this interaction is obtained by the analysis of bond stabilization in halides, oxides, sulphides and ionic dimers of rare gases. Most of this information comes from recent molecular beam experiments: when combined with the analysis of processes occurring at crossings between covalent and ionic states in alkali halides it leads to the characterization of the dependence of the charge transfer matrix element on basic physical properties of the interacting partners. The magnitude of the coupling matrix element is correlated to polarizabilities and charges. Its exponential decreasing with intermolecular distance is given in terms of ionization potentials and electron affinities, in the spirit of the study by Grice and Herschbach (Molec. Phys., 1973, 27, 159) on the long-range configuration interaction of ionic and covalent states. A proper representation is obtained both for the transition from van der Waals to chemical bonds and for the behaviour of different families of compounds, such as those of alkali halides and of rare-gas protonated systems.