Optimized partitioning in Rayleigh–Schrödinger perturbation theory

Abstract

Finite-order perturbation corrections are ambiguous since they depend on the partitioning of the Hamiltonian to a zero-order part and perturbation, and any chosen partitioning can be freely modified, e.g. by level shift projectors. To optimize low-order corrections, an approximate variational procedure is proposed to determine level shift parameters from the first-order Ansatz for the wavefunction. The resulting new partitioning scheme provides significantly better second-order results than those obtained by standard partitions like Epstein–Nesbet or Møller–Plesset. We treat the anharmonic oscillator and the atomic electron correlation energy in He, Be and Ne as numerical test cases.