Errors in approximate ionization energies due to the one-electron space truncation of the EKT eigenproblem

Abstract

Unless the approximate wavefunction of the parent system is expressed in terms of explicitly correlated basis functions, the finite size of the generalized Fock matrix is unlikely to be the leading source of the truncation error in the ionization energy [Formula: see text] produced by the EKT (extended Koopmans’ theorem) formalism. This conclusion is drawn from a rigorous analysis that involves error partitioning into the parent- and ionized-system contributions, the former being governed by asymptotic power laws when the underlying wavefunction is assembled from a large number of spinorbitals and the latter arising from the truncation of the infinite-dimensional matrix [Formula: see text] whose elements involve the 1-, 2-, and 3-matrices of the parent system. Quite surprisingly, the decay of the second contribution with the number n of the natural spinorbitals (NOs) employed in the construction of the truncated [Formula: see text] turns out to be strongly system-dependent even in the simplest case of the 1S states of two-electron systems, following the n−5 power law for the helium atom while exhibiting an erratic behavior for the H− anion. This phenomenon, which stems from the presence of the so-called solitonic natural spinorbitals among the NOs, renders the extrapolation of the EKT approximates of [Formula: see text] to the complete-basis-set limit generally unfeasible. However, attaining that limit is not contingent upon attempted reproduction of the ill-defined one-electron function known as “the removal orbital,” which does not have to be invoked in the derivation of EKT and whose expansion in terms of the NOs diverges.