It is known for a long time that the long range asymptotic behavior of the Hartree-Fock orbitals is different from that of the orbitals in the local potential. However, there is no consensus about observable physical effects associated with this asymptotics. Here we argue that weaker decrease of the Hartree-Fock orbitals at large distances is responsible for the positron annihilation on the inner shell electrons, which is observed experimentally.PACS numbers: 31.15.A-, 03.65.Ge
Long distance behaviour of electron orbitalsIt is sometimes assumed that exchange interaction between electrons is important only at short distances and can be neglected when one of the electrons is far from the origin. It is easy to see that this is not true if we consider long range asymptotics of an inner shell electron [1][2][3]. At large distances the exchange term for all occupied orbitals has the form r −ν φ v , where φ v is the outermost orbital with the highest energy ε v . The power ν depends on the leading multipolarity of the exchange interaction. The monopole component does not contribute to the asymptotics due to the orthogonality of the orbitals and for the dipole component of the exchange interaction ν = 2.This fact was first realized by Handy et al.[1], who showed that generally speaking asymptotic behavior of all Hartree-Fock orbitals is given by the exponential with the highest energy ε v (or the smallest binding energy):where ν i is specific for each orbital and r v is the radius of the outermost atomic orbital. We use atomic units h = m e = |e| = 1 unless stated otherwise. Because the monopole component of the exchange interaction does not contribute to the asymptotic behaviour, the expression (1) does not apply to the systems where only sorbitals are occupied.Later the asymptotic behaviour of the electron orbitals was reanalyzed by many authors [2][3][4][5][6]. Dzuba et al. [2] showed that the asymptote (1) holds for the relativistic Hatree-Fock-Dirac equations as well. The role of correlations were studied by Morrell et al. [4] and Katriel and Davidson [5], who demonstrated that Eq. (1) holds also for the natural orbitals φ nat i with nonzero occupation numbers. Natural orbitals are the eigenfunctions of the one electron density matrix ρ(x , x), where x ≡ r, σ and they can be found for any many electron wavefunction.Natural orbitals are mostly used in the context of the configuration interaction approach. For the corevalence correlations the many-body perturbation theory (MBPT) is usually more efficient. Within MBPT approach Flambaum [3] showed that Eq. (1) also holds for the Brueckber orbitals. The latter are solutions of the one particle equation with the correlation potential Σ added to the Hartree-Fock potential. The nonlocal part of the potential Σ decreases faster than the exchange potential and therefore does not change the long range behaviour of the Brueckner orbitals.In the solid state physics the long range exchange induced interaction is well known.For example, the Ruderman-Kittel-Kasuya-Yasida (RKKY) exc...