Correlation functions asymptotic behavior

However, it is known that the direct correlation functions have an exact long-range asymptotic form, arising due to intramolecular correlations in clusters formed via the association mechanism. This asymptotics is not included in the Percus-Yevick approximation. Other common liquid state approximations also do not provide correct asymptotic behavior of Ca ir). 

In Section II.D(4c), it was pointed out that, in treating correlation effects in a molecular system, it is of essential importance that the improved wave function leads to an energy curve having correct asymptotic behavior for separated atoms. It has been shown (Frost, Braunstein, and Schwemer 1948) that this condition may be fulfilled by a convenient choice of a correlation factor g. Let us consider the H2 molecule and a wave function of the type... 

A common problem for both methods lies in the use of potentials that do not possess the correct net attractiveness. This can have the consequence that continuum feamres appear shifted in energy. In particular, there is evidence that the LB94 exchange-correlation potential currently used for the B-spline calculations, although possessing the correct asymptotic behavior for ion plus electron, is too attractive, and near threshold features can then disappear below the ionization threshold. An empirical correction can be made, offsetting the energy scale, but this can mean that dynamics within a few electronvolts of threshold get an inadequate description or are lost. There is limited scope to tune the Xa potential, principally by adjustment of the assumed a parameter, but for the B-spline method a preferable alternative for the future may well be use of the SAOP functional that also has correct asymptotic behavior, but appears to be better calibrated for such problems [79]. 

In this nonvariational approach for the first term represents the potential of the exchange-correlation hole which has long range — 1/r asymptotics. We recognize the previously introduced splitup into the screening and screening response part of Eq. (69). As discussed in the section on the atomic shell structure the correct properties of the atomic sheU structure in v arise from a steplike behavior of the functional derivative of the pair-correlation function. However the WDA pair-correlation function does not exhibit this step structure in atoms and decays too smoothly [94]. A related deficiency is that the intershell contributions to E c are overestimated. Both deficiencies arise from the fact that it is very difficult to represent the atomic shell structure in terms of the smooth function p. Substantial improvement can be obtained however from a WDA scheme dependent on atomic shell densities [92,93]. In this way the overestimated intershell contributions are much reduced. Although this orbital-depen-... 

Levy identified the unknown part of the exact universal D functional as the correlation energy Ed D] and investigated a number of properties of c[ D], including scaling, bounds, convexity, and asymptotic behavior [11]. He suggested approximate explicit forms for Ec[ D] for computational purposes as well. Redondo presented a density-matrix formulation of several ab initio methods [26]. His generalization of the HK theorem followed closely Levy s... 

DPT schemes, which allow to calculate the electron affinities of atoms are based on the exact [59,60] and generalized (local) [61,62] exchange self-interaction-corrected (SIC) density functionals, treating the correlation separately in some approximation. Having better asymptotic behavior than GGA s, like in the improved SIC-LSD methods, one should obtain more... 

We can now calculate the rate of decay of initial correlations by making use of Eq. (69). The single-particle distribution function has the asymptotic behavior. 

A well known result states that the values of the discrete Fourier transform of a stationary random process are normally distributed complex variables when the length of the Fourier transform is large enough (compared to the decay rate of the noise correlation function) [Brillinger, 1981], This asymptotic normal behavior leads to a Rayleigh distributed magnitude and a uniformly distributed phase (see [McAulay and Malpass, 1980, Ephraim andMalah, 1984] and [Papoulis, 1991]). 

Density Functional Theory (DFT) has become a powerful tool for ab-initio electronic structure calculations of atoms, molecules and solids [1, 2, 3]. The success of DFT relies on the availability of accurate approximations for the exchange-correlation (xc) energy functional Exc or, equivalently, for the xc potential vxc. Though these quantities are not known exactly, a number of properties of the exact xc potential vxc(r) are well-known and may serve as valuable criteria for the investigation of approximate xc functionals. In this contribution, we want to focus on one particular property, namely the asymptotic behavior of the xc potential For finite systems, the exact xc potential vxc(r) is known to decrease like — 1/r as r —oo, reflecting also the proper cancellation of spurious self-interaction effects induced by the Hartree potential. 

It is in this context that exponentially correlated basis sets (EC or ECG) become particularly interesting, since such bases behave as if they contained high metric terms, but in a very compact form. With multiple nonlinear parameters, a trial wave function may be able to represent the wave function at the cusps accurately while retaining sufficient flexibility to correctly reproduce its asymptotic behavior. 

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