Perturbation-adapted perturbation theory.

A new general approach is introduced for defining an optimum zero-order Hamiltonian for Rayleigh-Schrödinger perturbation theory. Instead of taking the operator directly from a model problem, it is constructed to be a best fit to the exact Hamiltonian within any desired functional form. When applied to many-body perturbation theory for electrons, strongly improved convergence is observed in cases where the conventional Fock Hamiltonian leads to divergence or slow convergence.