Angular-Momentum Extrapolations to the Complete Basis Set Limit: Why and When They Work.

Abstract

The leading L-3 dependence of the errors in the energies computed with nuclei-centered basis sets comprising functions with angular momenta not exceeding L is rigorously proven for the 1Σ states of linear molecules and molecular ions with arbitrary even numbers of electrons. This major expansion of the domain of applicability over that offered by the routinely cited Hill asymptotic expression, which is valid only for the helium isoelectronic series, is accomplished with a formalism in which the off-diagonal cusp conditions for the one- and two-electron reduced density matrices play the central role. Despite being provided by these results with theoretical foundations more solid than ever before, the angular-momentum extrapolations to the complete basis set limit appear to work more by happenstance than mathematical rigor due to the poorly predictable variability in the prefactor multiplying the L-3 term and the far from negligible contributions from the terms involving higher powers of L-1.