Cavity correlation and bridge functions at high density and near the critical point: a test of second-order Percus–Yevick theory

ABSTRACT

Cavity correlation functions, pair correlation functions, and bridge functions for the Lennard-Jones fluid are calculated from first Percus–Yevick (PY) theory and second-order Percus– Yevick (PY2) theory, molecular dynamics, and grand canonical Monte Carlo techniques. We find that the PY2 theory is significantly more accurate than the PY theory, especially at high density and near the critical point. The pair correlation function near the critical point has the expected slowly decaying long-range behaviour. However, we do not observe any long-range behaviour in the bridge function for the state points near the critical point we have simulated. However, we do note that the bridge function, which is usually negative near r = 0, becomes positive as r → 0. This behaviour is seen for the bridge functions computed from both PY2 and molecular dynamics, but not from PY.     

Elastic Scattering of Electrons by a Cut-Off Coulomb Potential at Low Energies

Elastic scattering of electrons by cut-off Coulomb potential U_c(r) is investigated, where U_c(r) = 0, for r > r_c and U_c(r) = ?1/r + 1/r_c for r ≦ r_c. This is first considered in terms of classical, and later quantum mechanical (partial wave) methods in the low energy range 0 ≦ ? ? 1/r_c, where ? is the energy of the free electron. Scattering in this energy region displays a number of particular characteristics, such as back scattering, at certain energies. It can be concluded that some agreement does exist between the classical and quantum mechanical results.     

The effect of a surface on the dynamic and thermodynamic properties of S=1 Heisenberg ferromagnet with biquadratic exchange

Properties of semi-infinite (S=1) Heisenberg ferromagnet with biquadratic exchange were studied in terms of surface exchange (=I_S/I) and biquadratic coupling (a). It was shown that a strict correlation exists, depending on , between the type of surface spin waves (acoustic or optical) and the mean-field (MF) critical temperature, bulk (T_c) and surface T_c^S>T_c (for ). Within the framework of the Landau–Ginsburg theory for semi-infinite simple cubic ferromagnet, a detailed study is presented of the critical behaviour of the system, in particular in the vicinity of the tricritical point which is the consequence of the biquadratic interaction. It is shown that tricritical exponents satisfy exactly the scaling relations for d=3. The analysis of the spin–spin correlation function within the framework of the same theory, shows that there occurs the critical magnetic scattering of low-energy electrons (LEED) from the surface in the case , when the ordering temperature T_c^S is approached from above (from paramagnetic phase). In the opposite case, , there occurs no surface critical scattering. It was also shown that in the vicinity of the tricritical point, the biquadratic interaction increases the range of validity of the MF approximation.     

The penetrable sphere and related models of liquid—vapour equilibrium

The equation of state of the penetrable sphere model of liquid—vapour equilibrium is calculated by three different sequences of approximations; the first is based on the virial expansion of the equivalent two-component model in powers of the densities, the second on expansion in powers of the activity, and the third on a cumulant expansion of the configurational energy in powers of the reciprocal temperature. These sequences are examined both with the inclusion of all coefficients and with the sub-sets of coefficients appropriate to the first and second Percus-Yevick (PY) approximations. The first PY approximation gives a classical critical point whose density and temperature are accurately determined. The second PY and the complete set of coefficients yield badly-behaved series from which few conclusions can be drawn.

The penetrable sphere model is generalized to a wider class of potentials and one of these, in which the configurational energy is expressed in terms of gaussian functions is related to a two-component model of Helfand and Stillinger. It is more tractable than the original model and is examined by the same sequences of approximations. They have shown that the complete series leads to a non-classical critical point in their version of the model; here we show that the first PY approximation is classical but the second nonclassical.     

Virial series around non-null density: density dependence of virial coefficients

It is shown that the equation of state of fluid systems can be expanded around non-null densities if the well known virial series is generalized by considering its coefficients as density dependent. This in turn leads to a hierarchy of differential equations that describe the coefficients b_j (ρ). Starting from the already known equation of state for hard bodies in d = 0,1,2,3 dimensions this hierarchy is analysed and the behaviour of both the reducible b_j (ρ) and irreducible β～ _j (ρ) cluster integrals is discussed. New virial coefficients b_j (ρ) have been introduced with a simpler density dependence. Their asymptotic (j → ∞) behaviour is discussed.     

高次正幂与逆幂势函数的叠加的径向薛定谔方程的解析解

当薛定谔方程中出现高次非谐振子势，电偶极矩势，分子晶体势，极化等效势等高次正幂与逆幂势函数以及它们的叠加时，薛定谔方程的求解变得非常复杂，采用奇点邻域附近的级数解法与求解渐近解相结合，在多种相互作用幂函数紧密耦合的条件下，得到势函数为V(r)=a₁r⁶+a₂r²+a₃r^{-4关键词： 级数解法 幂势函数 径向波函数 渐近解}     

Classical spin liquid properties of the infinite-component spin vector model on a fully frustrated two dimensional lattice

Thermodynamic quantities and correlation functions (CFs) of the classical antiferromagnet on the checkerboard lattice are studied for the exactly solvable infinite-component spin-vector model, D↦∞. In contrast to conventional two-dimensional magnets with continuous symmetry showing extended short-range order at distances smaller than the correlation length, r ξ _c∝ exp(T ^*/T), correlations in the checkerboard-lattice model decay already at the scale of the lattice spacing due to the strong degeneracy of the ground state characterized by a macroscopic number of strongly fluctuating local degrees of freedom. At low temperatures, spin CFs decay as < >∝ 1/r ² in the range a ₀≪r≪ξ _c∝T ^-1/2, where a₀ is the lattice spacing. Analytical results for the principal thermodynamic quantities in our model are very similar with MC simulations, exact and analytical results for the classical Heisenberg model (D = 3) on the pyrochlore lattice. This shows that the ground state of the infinite-component spin vector model on the checkerboard lattice is a classical spin liquid. Received 16 November 2001 and Received in final form 12 February 2002     

The relative motion of membranes

The relative classical motion of membranes is governed by the equation (w _{β c} ^{α c} r ^βa ) _a = R _δγβ ^α r ^gb x ^δa p _a ^γ , where w is the hessian. This is a generalization of the geodesic deviation equation and can be derived from the lagrangian p · ṙ. Quantum mechanically the picture is less clear. Some quantizations of the classical equations are attempted so that the question as to whether the Universe started with a quantum fluctuation can be addressed.     

On shallow-deep instability of impurity level in semiconductors

The question of shallow-deep instability of the ground state of an impurity in a semiconductor is examined in terms of a model potential which is Coulombic at short distances (marked by r<b), and screened Coulomb at larger distances (r>;b). It is shown that for b larger than a critical value b_c the level rapidly becomes deeper, and the value of b_c depends strongly on the effective mass μ increasing rapidly with decreasing μ.     

Calculation of the radial distribution function of hard-sphere mixtures in the Percus-Yevick approximation

A formulation is given which permits the rapid mechanical computation of the three radial distribution functions g_ij (r) of a binary hard-sphere mixture to any distance r, in the Percus-Yevick (P-Y) approximation. The consistency of the P-Y equation of state obtained by various methods is discussed.     

Quadratic magnetoelectric effect and the role of the magnetocaloric effect in the magnetoelectric properties of multiferroic BaMnF<Subscript>4</Subscript>

The magnetoelectric effects in BaMnF₄ in magnetic fields up to 250 kOe are experimentally studied and theoretically analyzed using the magnetic symmetry of the crystal. The presence of quadratic magnetoelectric effect tensor components that correspond to the electric polarization components along the b and c axes indicates triclinic distortions in the monoclinic symmetry of the crystal. The anomalous dependence of the magnetic field-induced polarization (P _a (H _b )) can be related to the pyroelectric effect caused by magnetocaloric heating of the crystal. The measured torque curves point to a 9° deviation of the spin orientation from the b axis.     

Distribution function for large velocities of a two-dimensional gas under shear flow

The high-velocity distribution of a two-dimensional dilute gas of Maxwell molecules under uniform shear flow is studied. First we analyze the shear-rate dependence of the eigenvalues governing the time evolution of the velocity moments derived from the Boltzmann equation. As in the three-dimensional case discussed by us previously, all the moments of degreek⩾4 diverge for shear rates larger than a critical valuea _c ^(k) , which behaves for largek asa _c ^(k) ∼k ⁻¹. This divergence is consistent with an algebraic tail of the formf(V) ∼V ^−4-σ(a), where σ is a decreasing function of the shear rate. This expectation is confirmed by a Monte Carlo simulation of the Boltzmann equation far from equilibrium.     

Black holes with metric and fields of the same form

We present two rotating black hole solutions with axion ξ, dilaton f{\phi} and two U(1) vector fields. Starting from a non-rotating metric with three arbitrary parameters, which we have found previously, and applying the “Newman–Janis complex coordinate trick” we get a rotating metric g _μν with four arbitrary parameters namely the mass M, the rotation parameter a and the charges electric Q _E and magnetic Q _M . Then we find a solution of the equations of motion having this g _μν as metric. Our solution is asymptotically flat and has angular momentum J = M a, gyromagnetic ratio g = 2, two horizons, the singularities of the solution of Kerr, axion and dilaton singular only when r = a cos θ = 0 etc. By applying to our solution the S-duality transformation we get a new solution, whose axion, dilaton and vector fields have one more parameter. The metrics, the vector fields and the quantity l = x+ie^-2f{\lambda=\xi+ie^{-2\phi}} of our solutions and the solution of: Sen for Q _E , Sen for Q _E and Q _M , Kerr–Newman for Q _E and Q _M , Kerr, Reference Kyriakopoulos [Class. Quantum Grav. 23:7591, 2006, Eqs. (54–57)], Shapere, Trivedi and Wilczek, Gibbons–Maeda–Garfinkle–Horowitz–Strominger, Reissner–Nordstr?m, Schwarzschild are the same function of a, and two functions ρ ² = r(r + b) + a ² cos² θ and Δ = r(r + b) − 2Mr + a ² + c, of a, b and two functions for each vector field, and of a, b and d respectively, where a, b, c and d are constants. From our solutions several known solutions can be obtained for certain values of their parameters. It is shown that our two solutions satisfy the weak the dominant and the strong energy conditions outside and on the outer horizon and that all solutions with a metric of our form, whose parameters satisfy some relations satisfy also these energy conditions outside and on the outer horizon. This happens to all solutions given in the “Appendix”. Mass formulae for our solutions and for all solutions which are mentioned in the paper are given. One mass formula for each solution is of Smarr’s type and another a differential mass formula. Many solutions with metric, vector fields and λ of the same functional form, which include most physically interesting and well known solutions, are listed in an “Appendix”.     

Dynamic Mechanical Behavior of Ordered Off-Stoichiometric Polyurethane Systems at the Gel Point Threshold

Dynamic mechanical and thermal behavior of ordered off-stoichiometric polyurethane (PU) systems, before and after the gel point, based on the mesogenic diol 6,6′;-[ethylenebis(1,4-phenyleneoxy)]dihexan-1-ol (D),2(4)-methyl-1,3-phenylene diisocyanate (DI), and poly(oxypropylene)triol (T) were studied. Polymer samples were prepared at various initial molar ratios of the reactive groups, r = [OH]_T/[NCO]_DI/[OH]_D, ranging from 1/10/9 to 5/10/9 (the ratio [NCO]_DI/[OH]_D = 10/9 was constant); the total mole ratio of hydroxy (OH) and isocyanate (NCO) groups, rOH = [OH]/[NCO] = ([OH]_D)/[NCO]_DI,changed from 1 to 1.4. Dynamic mechanical measurements during the curing reaction showed that the power law parameters that characterize the critical gel state (gel strength S and relaxation exponent n) are dependent on the initial composition (the ratio r _OH). The gel-point critical ratio of reactive groups r^c _OH, found during curing in the ordered state of the diol (at low curing temperature), has revealed that the critical gel (CG) structure is determined by a contribution of strong physical interactions as well as chemical junctions and does not correspond to pure chemical gelation (CG structure formed at low temperature exhibits flow at elevated temperatures in the isotropic state). This fact suggests that formation of the mesophase enhances the connectivity of the molecular structure at the gel point. Dynamic mechanical behavior of fully cured chemical networks (r _OH < r _OH ^c ) and un-cross-linked (r _OH > r _OH ^c ) samples (and a CG sample) has also been investigated. Decreasing the r_OH ratio (increasing concentration of chemical cross-links in the systems) inhibits conformational rearrangements required for ordering; at the same time, the intensity of the slow relaxation process in the rubbery region decreases.     

Statistical Mechanical Theory of Bimolecular Reaction. Derivation of the Arrhenius Law. Characterization of a Catalyst

A statistical mechanical theory is developed for gas-phase bimolecular (binary) reactions: AB ⇌ A + B. Based on the activated-complex hypotheses, and expression for the association rate constant k_a is derived: k_a = k*_{AB* → AB} (QAB*/q_A+B), where k*_{AB* →AB} is the rate constant for the transition from the activated state AB* to the molecular state AB, and qx is the equilibrium occupation probability for state X. The three states (AB, AB*, A + B) are defined by three regions of the energyseparation plane for the relative motion of the reactant pair (A, B). If the interatomic potential has a critical barrier ϵ_c at separation r_c and an attractive well with depth ϵ_b (ϵ_c, ϵ_b > k_BT) computations of the q_AB*/q_{A +B} generate an Arrhenius-Boltzmann factor exp (—ϵ_c/k_BT). The virtual rate constant k*_{AB* →AB} is calculated by assuming that the reactant pair reaching the activated state AB* with the separation r < r_c and the energy E > _c moves on to the molecular state AB only if it loses part of its radial kinetic energy with the aid of third body (catalyst or collision) and is trapped by the potential well. With no catalysts present, this constant is approximately given by k*_{AB* →AB} =πd′²v′ R′⁻³, where v′ is the thermal center-of-mass speed, and d′ and R′ are respectively the collision-sphere radius and the mean distance between AB* and any molecule (A, B, AB or AB*). For binary dissociation, the rate constant k_d is given by k_d = k*_{AB* →A+B} q_AB*/q_AB), which generates exp [—(ϵ_c + ϵ_b)/k_BT]. A catalyst for binary reaction is assumed to act as a mediator, facilitating the energy exchange between the radial and rotational modes of motion. Additionally for association only, it also acts as a confinement agent, preventing the pair from flying away from each other. Connections with the collision theory and the activated complex theory are discussed critically.     

Stokes–Leibenson problem for Hele-Shaw flow: a critical set in the space of contours

The Stokes–Leibenson problem for Hele-Shaw flow is reformulated as a Cauchy problem of a nonlinear integro-differential equation with respect to functions a and b, linked by the Hilbert transform. The function a expresses the evolution of the coefficient longitudinal strain of the free boundary and b is the evolution of the tangent tilt of this contour. These functions directly reflect changes of geometric characteristics of the free boundary of higher order than the evolution of the contour point obtained by the classical Galin–Kochina equation. That is why we managed to uncover the reason of the absence of solutions in the sink-case if the initial contour is not analytic at at least one point, to prove existence and uniqueness theorems, and also to reveal a certain critical set in the space of contours. This set contains one attractive point in the source-case corresponding to a circular contour centered at the source-point. The main object of this work is the analysis of the discrete model of the problem. This model, called quasi-contour, is formulated in terms of functions corresponding to a and b of our integro-differential equation. This quasi-contour model provides numerical experiments which confirm the theoretical properties mentioned above, especially the existence of a critical subset of co-dimension 1 in space of quasi-contours. This subset contains one attractive point in the source-case corresponding to a regular quasi-contour centered at the source-point. The main contribution of our quasi-contour model concerns the sink-case: numerical experiments show that the above subset is attractive. Furthermore, this discrete model allows to extend previous results obtained by using complex analysis. We also provide numerical experiments linked to fingering effects.     

A lattice hydrodynamical model considering turning capability

A new two-dimensional lattice hydrodynamic model considering the turning capability of cars is proposed. Based on this model, the stability condition for this new model is obtained by using linear stability analysis. Near the critical point, the modified KdV equation is deduced by using the nonlinear theory. The results of numerical simulation indicate that the critical point a c increases with the increase of the fraction p of northbound cars which continue to move along the positive y direction for c = 0.3, but decreases with the increase of p for c = 0.7. The results also indicate that the cars moving along only one direction (eastbound or northbound) are most stable.