Two-particle integrals

Theorem 2 For a Coulomb Hamiltonian, in an actual configuration-interaction -type calculation with one-particle square-integrable, analytic functions as basis sets, all overlap, one- and two-particle integrals remain invariant under transformations of the type u r)... 

In the graphical representation of the integral shown above, a line represents the Mayer function f r.p between two particles and j. The coordinates are represented by open circles that are labelled, unless it is integrated over the volume of the system, when the circle representing it is blackened and the label erased. The black circle in the above graph represents an integration over the coordinates of particle 3, and is not labelled. The coefficient of is the sum of tln-ee tenns represented graphically as... 

We will describe integral equation approximations for the two-particle correlation fiinctions. There is no single approximation that is equally good for all interatomic potentials in the 3D world, but the solutions for a few important models can be obtained analytically. These include the Percus-Yevick (PY) approximation [27, 28] for hard spheres and the mean spherical (MS) approximation for charged hard spheres, for hard spheres with point dipoles and for atoms interacting with a Yukawa potential. Numerical solutions for other approximations, such as the hypemetted chain (EfNC) approximation for charged systems, are readily obtained by fast Fourier transfonn methods... 

Second-Order Integral Equations for Associating Fluids As mentioned above in Sec. II A, the second-order theory consists of simultaneous evaluation of the one-particle (density profile) and two-particle distribution functions. Consequently, the theory yields a much more detailed description of the interfacial phenomena. In the case of confined simple fluids, the PY2 and HNC2 approaches are able to describe surface phase transitions, such as wetting and layering transitions, in particular see, e.g.. Ref. 84. 

In the numerical solution the matrix structure is evaluated from Eqs. (44)-(46). Then Eqs. (47)-(49) with corresponding closure approximations are solved. Details of the solution have been presented in Refs. 32 and 33. Briefly, the numerical algorithm uses an expansion of the two-particle functions into a Fourier-Bessel series. The three-fold integrations are then reduced to sums of one-dimensional integrations. In the case of hard-sphere potentials, the BGY equation contains the delta function due to the derivative of the pair interactions. Therefore, the integrals in Eqs. (48) and (49) are onefold and contain the contact values of the functions... 

The contact force between two particles is now determined by only five parameters normal and tangential spring stiffness kn and kt, the coefficient of normal and tangential restitution e and et, and the friction coefficient /if. In principle, kn and k, are related to the Young modulus and Poisson ratio of the solid material however, in practice their value must be chosen much smaller, otherwise the time step of the integration needs to become unpractically small. The values for kn and k, are thus mainly determined by computational efficiency and not by the material properties. More on this point is given in the Section III.B.7 on efficiency issues. So, finally we are left with three collision parameters e, et, and which are typical for the type of particle to be modeled. 

One such systematic generalization was obtained by Cohen,8 whose method is now given the point of departure was the expansion in clusters of the non-equilibrium distribution functions. This procedure is formally analogous to the series expansion in the activity where the integrals of the Ursell cluster functions at equilibrium appear in the coefficients. Cohen then obtained two expressions in which the distribution functions of one and two particles are given in terms of the solution of the Liouville equation for one particle. The elimination of this quantity between these two expressions is a problem which presents a very full formal analogy with the elimination (at equilibrium) of the activity between the Mayer equation for the concentration and the series... 

The Laplace-Young equation refers to a spherical phase boundary known as the surface of tension which is located a distance from the center of the drop. Here the surface tension is a minimum and additional, curvature dependent, terms vanish (j ). The molecular origin of the difficulties, discussed in the introduction, associated with R can be seen in the definition of the local pressure. The pressure tensor of a spherically symmetric inhomogeneous fluid may be computed through an integration of the one and two particle density distributions. 

Model Hartree-Fock calculations which include only the electrostatic interaction in terms of the Slater integrals F0, F2, F and F6, and the spin-orbit interaction , result in differences between calculated and experimentally observed levels596 which can be more than 500 cm-1 even for the f2 ion Pr3. However, inclusion of configuration interaction terms, either two-particle or three-particle, considerably improves the correlations.597,598 In this way, an ion such as Nd3+ can be described in terms of 18 parameters (including crystal field... 

For classical line shape calculations one needs the induced dipole moment as function of time, p(R(t)), averaged over angular momenta and speeds of relative motion. In other words, one solves Newton s equation of motion, or one of its integrals, of the two-particle system. After suitable averaging, one obtains the spectral profile by Fourier transform. 

Keeping in mind the physical meaning of single- and two-particle densities, equations (2.3.58) to (2.3.61), we can rewrite now equations (4.1.13) in a form similar to the standard chemical kinetics (Section 2.1). To do it, let us first transform the integral expression... 

Once the integration is performed, it can be easily shown that ojq12 oc an-It has been already discussed (see Section XIII) that the contribution from the three-particle contribution to the binary time constant of the friction is small thus for simplicity the analysis for is performed considering the contribution only from the two-particle term. Thus the second term in Eq. (120) is neglected and the angular integration in the first term is performed. This reduces Eq. (120) to the following form ... 

Mode coupling theory of binary mixtures where the constituents are of rather different sizes is a challenging task, as we have already discussed while addressing the mass depenence of diffusion. In addition to the problem with proper formulation of mode coupling terms, there is an additional difficulty of the nonavailability of the equilibrium two-particle correlation functions The existing integral equation theories become unstable when the size ratio exceeds a certain (low) value, like 1.5 or so [195],... 

We will carry out our program in two steps. In this section we will derive the two-particle density operator Fn in a three-particle collision approximation for the application in the collision integral of Fl. As compared with Section II.2, the main difference will be the occurrence of bound states and, especially, the generalization of the asymptotic condition, which now has to account for bound states too. For the purpose of the application in the kinetic equation of the atoms (bound states) we need an approximation of the next-higher-order density matrix, that is, F 23 This quantity will be determined under inclusion of certain four-particle interaction. 

The two-particle Boltzmann collision term if and the three-particle contribution for k = 0 were considered in Section II. It was possible to express those collision integrals in terms of the two- and three-particle scattering matrices. It is also possible to introduce the T matrix in if for the channels k = 1, 2,3, that is, in those cases where three are asymptotically bound states. Here we use the multichannel scattering theory, as outlined in Refs. 9 and 26. 

Let us first consider Eq. (3.68) for the distribution function of free particles. The contribution of the two-particle collision then gives the well-known Landau collision integral... 

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