Series expansions for an exact two-electron wave function in terms of Löwdin's renormalized natural orbitals

Abstract

In recent developments on the pair density needed to treat the non-Hartree-Fock-like part of interparticle repulsion, the natural orbitals and sign-correct expansion coefficients play a central role. Since, in principle, an infinite number of natural orbitals must be included, the convergence of expectation values due to finite-term approximations is an important issue. Here we discuss quantitatively this convergence problem based on an exactly solvable two-electron model atom, where the Schrödinger wave function for the ground state is expressible in terms of Löwdin's natural orbitals and sign-correct expansion coefficients. Using properly renormalized truncated series expansions for such an exact decomposition, the corresponding expectation values of the Schrödinger Hamiltonian are calculated analytically. A rapid and uniform convergence is found in these expectation values at given values of the coupling in the interparticle repulsion. © 2012 American Physical Society.