Singularities of Møller-Plesset energy functions

Abstract

The convergence behavior of Møller-Plesset (MP) perturbation series is governed by the singularity structure of the energy, with the energy treated as a function of the perturbation parameter. Singularity locations, determined from quadratic approximant analysis of high-order series, are presented for a variety of atoms and small molecules. These results can be used as benchmarks for understanding the convergence of low-order methods such as MP4 and for developing and testing summation methods that model the singularity structure. The positions and types of singularities confirm previous qualitative predictions based on functional analysis of the Schrodinger equation.